Method of purifying vinyl polymer

ABSTRACT

The present invention provides a method of purifying a vinyl polymer to be used as a component of a composition capable of undergoing hydrosilylation. 
     The present invention provides a vinyl polymers obtainable by atom transfer radical polymerization can be purified economically and efficiently by adsorption treatment using an acidic adsorbent and a basic adsorbent combinedly, with the result that the reactivity in hydrosilylation thereof is improved. Thus, the polymers can be used as components in hydrosilylation reaction-susceptible compositions.

TECHNICAL FIELD

The present invention relates to a method of purifying vinyl polymers,vinyl polymers, a hydrosilylation reaction-susceptible composition, anda curable composition.

BACKGROUND ART

The hydrosilylation reaction is utilized in functional group conversion,crosslinking and other reactions and is one of very useful reactionsfrom the industrial viewpoint. It is known, for example, that a polymerhaving an alkenyl group as a functional group at a molecular chainterminus can be crosslinked and cured to give cured products excellentin heat stability, durability and the like properties when a hydrosilylgroup-containing compound is used as a curing agent, and that when analkenyl group-terminated polymer is reacted with a a hydrosilylgroup-containing compound having a crosslinkable silyl group, acrosslinkable silyl group-terminated polymer is produced. Thesehydrosilylation reactions proceed upon heating, and a hydrosilylationcatalyst is added for causing the reactions to proceed more rapidly.Such hydrosilylation catalyst includes radical initiators, such asorganic peroxides and azo compounds, and transition metal catalysts. Inparticular, it is known that when a transition metal catalyst is used ina catalytic amount, the hydrosilylation can be allowed to proceedrapidly.

On the other hand, living polymerization is generally known as a precisemethod of polymer synthesis. A feature of living polymerization is thatnot only the molecular weight and molecular weight distribution can becontrolled but also polymers definite in terminal structure can beobtained. Therefore, living polymerization may be mentioned as one ofeffective methods of functional group introduction at a polymer terminusor termini. In radical polymerization as well, polymerization systems inwhich living polymerization is possible have recently been found and,thus, advanced studies on living radical polymerization are underway. Inparticular, when atom transfer radical polymerization is utilized,polymers narrow in molecular weight distribution can be obtained. Asexamples of atom transfer radical polymerization systems, there may bementioned polymerization systems using, as an initiator, an organichalide or halogenated sulfonyl compound and, as a catalyst, a metalcomplex with a central atom selected from among elements of the group 8,9, 10, and 11 of the periodic table of the elements. (For example, seeMatyjaszewski et al., J. Am. Chem. Soc., 1995, 117, 5614,Macromolecules, 1995, 28, 7901, Science, 1996, 272, 866, or Sawamoto etal., Macromolecules, 1995, 28, 1721).

However, the transition metal complex, namely the polymerizationcatalyst, remains in the vinyl polymers produced by atom transferradical polymerization, producing such problems as coloration of thepolymers, influences on the physical properties thereof, andenvironmental safety problems. For example, in the case of alkenylgroup-terminated vinyl polymers produced by utilizing the atom transferradical polymerization technique, the residual catalyst and the likeserve as catalyst poisons in the hydrosilylation reaction and, thus, thehydrosilylation reaction is inhibited, producing a problem in that theexpensive transition metal catalyst is required in larger amounts.

The present inventors previously found that the hydrosilylation activityof vinyl polymers obtainable by atom transfer radical polymerization canbe improved by purifying the polymers by bringing them into contact withan adsorbent such as aluminum silicate (Japanese Kokai PublicationHei-11-193307). On that occasion, however, the adsorbent is required inlarge amounts, causing such problems as an environmental impact by thewaste and an adsorbent-related increase in purification cost. It is anobject of the present invention to solve these problems and provide aneconomical and efficient method of purifying vinyl polymers as well as apolymer and a composition capable of reacting in the manner ofhydrosilylation.

SUMMARY OF THE INVENTION

(1) The present invention relates to a method of purifying a vinylpolymer obtainable by atom transfer radical polymerization of a vinylmonomer(s) using a transition metal complex as a polymerization catalyst

which method comprises bringing the vinyl polymer into contact with anacidic adsorbent and a basic adsorbent in a total amount of 0.01 to 10parts by weight per 100 parts by weight of the vinyl polymer.

(2) The present invention also relates to a method of purifying a vinylpolymer as mentioned above,

wherein the acidic adsorbent and/or basic adsorbent is an inorganicadsorbent;

a method of purifying a vinyl polymer as mentioned above,

wherein the acidic adsorbent is activated terra alba or aluminumsilicate;

a method of purifying a vinyl polymer as mentioned above,

wherein the acidic adsorbent is aluminum silicate;

a method of purifying a vinyl polymer as mentioned above,

wherein the basic adsorbent is activated alumina, or a hydrotalcite; and

a method of purifying a vinyl polymer as mentioned above,

wherein the basic adsorbent is a hydrotalcite.

(3) The present invention further relates to a method of purifying avinyl polymer as mentioned above,

wherein a solution of the vinyl polymer with a vinyl polymerconcentration of not less than 90% by weight is brought into contactwith an acidic adsorbent and/or a basic adsorbent; and

a method of purifying a vinyl polymer as mentioned above,

wherein the vinyl polymer is brought into contact with an acidicadsorbent and/or a basic adsorbent without using any solvent.

(4) The present invention further relates to a method of purifying avinyl polymer as mentioned above,

wherein the vinyl polymer has a halogen group;

a method of purifying a vinyl polymer as mentioned above,

wherein the vinyl polymer has an alkenyl group;

a method of purifying a vinyl polymer as mentioned above,

wherein the vinyl polymer is one obtainable by producing a halogengroup-containing vinyl polymer by atom transfer radical polymerizationand converting the halogen group to a substituent other than the halogengroup by a nucleophilic substitution reaction; and

a method of purifying a vinyl polymer as mentioned above,

wherein the vinyl polymer is brought into contact with an acidicadsorbent and/or a basic adsorbent without removing, from the polymer,the unreacted nucleophilic reagent and/or the halide resulting from thenucleophilic substitution reaction.

(5) The present invention further relates to a method of purifying avinyl polymer as mentioned above,

wherein the central atom of the transition metal complex is copper;

a method of purifying a vinyl polymer as mentioned above,

wherein a triamine compound is used as a ligand to the catalyst in theatom transfer radical polymerization; and

a method of purification as mentioned above,

wherein the acidic adsorbent and basic adsorbent are used in a totalamount of 0.1 to 10 parts by weight per 100 parts by weight of the vinylpolymer.

(6) The present invention further relates to a vinyl polymer

which is obtainable by the method of purifying a vinyl polymer asmentioned above;

a hydrosilylation-susceptible composition

which comprises (A) the vinyl polymer obtainable by any of the abovemethods of purifying a vinyl polymer;

a hydrosilylation-susceptible composition

which comprises (A) the vinyl polymer obtainable by any of the abovemethods of purifying a vinyl polymer and (B) a hydrosilylgroup-containing compound; and

a hydrosilylation-susceptible composition

which comprises (A) the vinyl polymer obtainable by any of the abovemethods of purifying a vinyl polymer, (B) a hydrosilyl group-containingcompound and (C) a platinum catalyst.

(7) The present invention further relates to a vinyl polymer

which is obtainable by subjecting the above hydrosilylation-susceptiblecomposition to hydrosilylation;

a crosslinkable silyl group-containing vinyl polymer

which is obtainable by subjecting the above hydrosilylation-susceptiblecomposition to hydrosilylation;

a cured product

which is obtainable by subjecting the above hydrosilylation-susceptiblecomposition to hydrosilylation;

a molded article which is obtainable by subjecting the abovehydrosilylation-susceptible composition to hydrosilylation; and

a method of producing vinyl polymers

which comprises using any of the above methods of purifying a vinylpolymer.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method of purifying a vinyl polymerobtainable by atom transfer radical polymerization of a vinyl monomer(s)using a transition metal complex as a polymerization catalyst

which method comprises bringing the. vinyl polymer into contact with anacidic adsorbent and a basic adsorbent in a total amount of 0.01 to 10parts by weight per 100 parts by weight of the vinyl polymer. The vinylpolymer to be purified is one produced by utilizing the technique ofatom transfer radical polymerization.

Atom Transfer Radical Polymerization

First, the atom transfer radical polymerization technique is describedin detail. The technique of atom transfer radical polymerization, soreferred to herein, is one of living radical polymerization techniquesand comprises polymerizing a vinyl monomer(s) using an organic halide orhalogenated sulfonyl compound as an initiator and, as a catalyst, ametal complex having a transition metal as a central atom. As specificreferences, there may be mentioned Matyjaszewski et al.: J. Am. Chem.Soc., 1995, vol. 117, page 5614, Macromolecules, 1995, vol. 28, page7901, Science, 1996, vol. 272, page 866, WO 96/30421, WO 97/18247, WO98/01480, WO 98/40415, and Sawamoto et al.: Macromolecules, 1995, vol.28, page 1721, Japanese Kokai Publication Hei-09-208616 and JapaneseKokai Publication Hei-08-41117, among others.

In this atom transfer radical polymerization, an organic halide, inparticular a highly reactive carbon-halogen bond-containing organichalide (e.g. a carbonyl compound having a halogen at an α-position or acompound having a halogen at a benzyl position), a halogenated sulfonylcompound or the like is used as an initiator. Specific examples are asfollows:C₆H₅—CH₂X, C₆H₅—C(H)(X)CH₃, C₆H₅—C(X)(CH₃)₂(in the above chemical formulas, C₆H₅ is a phenyl group and X is achlorine, bromine or iodine atom);R³—C(H)(X)—CO₂R⁴, R³—C(CH₃)(X)—CO₂R⁴, R³—C(H)(X)—C(O)R⁴,R³—C(CH₃)(X)—C(O)R⁴(in the above formulas, R₃ and R⁴ each is a hydrogen atom or an alkyl,aryl or aralkyl group containing 1 to 20 carbon atoms and X is achlorine, bromine or iodine atom);R³—C₆H₄—SO₂X(in the above formula, R³ is a hydrogen atom or an alkyl, aryl oraralkyl group containing 1 to 20 carbon atoms and X is a chlorine,bromine or iodine atom); and the like.

When atom transfer radical polymerization of a vinyl monomer(s) iscarried out using an organic halide or halogenated sulfonyl compound asan initiator, a vinyl polymer having a terminal structure represented bythe general formula (1):—C(R¹)(R²)(X)  (1)wherein R¹ and R² each represents a group bound to an ethylenicallyunsaturated group of a vinyl monomer and X represents a chlorine,bromine or iodine atom is obtained.

An organic halide or halogenated sulfonyl compound having a furtherspecific reactive functional group not associated with initiating thepolymerization in addition to the functional group for initiating thepolymerization may also be used as the initiator in atom transferradical polymerization. In such case, vinyl polymers having the furtherspecific reactive functional group at one main chain terminus and aterminal structure represented by the general formula (1) at the othermain chain terminus are produced. As such specific reactive functionalgroup, there may be mentioned alkenyl, crosslinkable silyl, hydroxyl,epoxy, amino and amide groups, among others. By utilizing the reactivityof such reactive functional group, it becomes possible to introduce anappropriate other functional group into the vinyl polymer through one ora plurality of reaction steps.

The alkenyl group-containing organic halide is not particularlyrestricted but includes, among others, those having a structurerepresented by the general formula (2):R⁶R⁷C(X)—R⁸—R⁹—C(R⁵)═CH₂  (2)wherein R⁵ is a hydrogen atom or a methyl group, R⁶ and R⁷ each is ahydrogen atom or a univalent alkyl, aryl or aralkyl group containing 1to 20 carbon atoms and such R⁶ and R⁷ groups may be bound together atthe respective other ends, R⁸ is —C(O)O— (ester group), —C(O)— (ketogroup) or an o-, m- or p-phenylene group, R⁹ is a direct bond or abivalent organic group containing 1 to 20 carbon atoms, which maycontain one or more ether bonds, and X is a chlorine, bromine or iodineatom.

As specific examples of the substituent R⁶ and R⁷, there may bementioned a hydrogen atom, and methyl, ethyl, n-propyl, isopropyl,butyl, pentyl, hexyl and like groups. R⁶ and R⁷ may be connected to eachother at the respective other ends to form a cyclic skeleton.

As specific examples of the alkenyl-containing organic haliderepresented by the general formula (2), there may be mentioned thefollowing:XCH₂C(O)O(CH₂)_(n)CH═CH₂, H₃CC(H)(X)C(O)O(CH₂)_(n)CH═CH₂,(H₃C)₂C(X)C(O)O(CH₂)_(n)CH═CH₂, CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)CH═CH₂,

(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20);XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,

(in the above formulas, X is a chlorine, bromine or iodine atom, n is aninteger of 1 to 20 and m is an integer of 0 to 20);o-, m-, p-XCH₂—C₆H₄—(CH₂)_(n)—CH═CH₂,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20);o-, m-, p-XCH₂—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂(in the above formulas, X is a chlorine, bromine or iodine atom, n is aninteger of 1 to 20 and m is an integer of 0 to 20);o-, m-, p-XCH₂—C₆H₄—O—(CH₂)_(n)—CH═CH₂,o-, m-, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20); ando-, m-, p-XCH₂—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o-, m-, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(n)—CH═CH₂(in the above formulas, X is a chlorine, bromine or iodine atom, n is aninteger of 1 to 20 and m is an integer of 0 to 20).

As the alkenyl group-containing organic halide, there may further bementioned compounds represented by the general formula (3):H₂C═C(R⁵)—R⁹—C(R⁶)(X)—R¹⁰—R⁷  (3)wherein R⁵, R⁶, R⁷, R⁹ and X are as defined above and R¹⁰ represents adirect bond, —C(O)O— (ester group), —C(O)— (keto group) or an o-, m- orp-phenylene group.

R⁹ is a direct bond or a bivalent organic group (which may contain oneor more ether bonds) containing 1 to 20 carbon atoms. When it is adirect bond, a vinyl group is bound to the carbon atom to which ahalogen is bound, whereby an allyl halide compound is formed. In thiscase, the carbon-halogen bond is activated by the neighboring vinylgroup, so that R¹⁰ is not always required to be a C(O)O or phenylenegroup, for instance, but may be a direct bond. When R⁹ is other than adirect bond, R¹⁰ should preferably be a C(O)O, C(O) or phenylene groupso that the carbon-halogen bond may be activated.

Specific examples of the compound of general formula (3) are as follows:CH₂═CHCH₂X, CH₂═C(CH₃)CH₂X, CH₂═CHC(H)(X)CH₃,CH₂═C(CH₃)C(H)(X)CH₃, CH₂═CHC(X)(CH₃)₂, CH₂═CHC(H)(X)C₂H₅,CH₂═CHC(H)(X)CH(CH₃)₂, CH₂═CHC(H)(X)C₆H₅, CH₂═CHC(H)(X)CH₂C₆H₅,CH₂═CHCH₂C(H)(X)—CO₂R, CH₂═CH(CH₂)₂C(H)(X)—CO₂R,CH₂═CH(CH₂)₃C(H)(X)—CO₂R, CH₂═CH(CH₂)₈C(H)(X)—CO₂R,CH₂═CHCH₂C(H)(X)—C₆H₅, CH₂═CH(CH₂)₂C(H)(X)—C₆H₅,CH₂═CH(CH₂)₃C(H)(X)—C₆H₅(in the above formulas, X is a chlorine, bromine or iodine atom and R isan alkyl, aryl or aralkyl group containing 1 to 20 carbon atoms), etc.

The following may be mentioned as specific examples of the alkenylgroup-containing halogenated sulfonyl compound:o-, m-, p-CH₂═CH—(CH₂)_(n)—C₆H₄—SO₂X,o-, m-, p-CH₂═CH—(CH₂)_(n)—O—C₆H₄—SO₂X(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20); etc.

The above-mentioned crosslinkable silyl group-containing organic halideis not particularly restricted but includes, among others, compoundshaving a structure represented by the general formula (4):R⁶R⁷C(X)—R⁸—R⁹—C(H)(R⁵)CH₂—[Si(R¹¹)_(2−b)(Y)_(b)O]_(m)—Si(R¹²)_(3−a)(Y)_(a)  (4)wherein R⁵, R⁶, R⁷, R⁸, R⁹ and X are as defined above, R¹¹ and R¹² eachrepresents an alkyl, aryl or aralkyl group containing 1 to 20 carbonatoms or a triorganosiloxy group represented by (R′)₃SiO— (in which R′is a univalent hydrocarbon group containing 1 to 20 carbon atoms and thethree R′ groups may be the same or different) and, when there are two ormore R¹¹ or R¹² groups, they may be the same or different; Y representsa hydroxyl group or a hydrolyzable group and, when there are two or moreY groups, they may be the same or different; a represents 0, 1, 2 or 3,b represents 0, 1 or 2, and m is an integer of 0 to 19 provided that therelation a+mb≧1 is satisfied.

Thehydrolyzable group includes, among others, a hydrogen atom, and thosegroups in general use, such as alkoxy, acyloxy, ketoximate, amino,amide, aminoxy, mercapto and alkenyloxy groups. Among these, alkoxy,amide and aminoxy groups are preferred. Alkoxy groups are particularlypreferred because of their mild hydrolyzability and easy handleability.

Specific examples of the compound of general formula (4) are as follows:XCH₂C(O)O(CH₂)_(n)Si(OCH₃)₃, CH₃C(H)(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,(CH₃)₂C(X)C(O)O(CH₂)_(n)Si(OCH₃)₃, XCH₂C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,CH₃C(H)(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,(CH₃)₂C(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20);XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂(in the above formulas, X is a chlorine, bromine or iodine atom, n is aninteger of 1 to 20 and m is an integer of 0 to 20);o-, m-, p-XCH₂—C₆H₄—(CH₂)₂Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,o-, m-, p-XCH₂—C₆H₄—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,o-, m-, p-XCH₂—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-XCH₂—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₃—Si(OCH₃)₃,o-, m-, p-XCH₂—C₆H₄—O—(CH₂)₂—O—(CH₂)₃—Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃(in the above formulas, X is a chlorine, bromine or iodine atom); etc.

As further examples of the above-mentioned crosslinkable silylgroup-containing organic halide, there may be mentioned compounds havinga structure represented by the general formula (5):(R¹²)_(3−a)(Y)_(a)Si—[OSi(R¹¹)_(2−b)(Y)_(b)]_(m)—CH₂—C(H)(R⁵)—R⁹—C(R⁶)(X)—R¹⁰—R⁷  (5)wherein R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹¹, R¹², a, b, m, X and Y are as definedabove.

Specific examples of such compound are as follows:(CH₃O)₃SiCH₂CH₂C(H)(X)C₆H₅, (CH₃O)₂(CH₃)SiCH₂CH₂C(H)(X)C₆H₅,(CH₃O)₃Si(CH₂)₂C(H)(X)—CO₂R, (CH₃O)₂(CH₃)Si(CH₂)₂C(H)(X)—CO₂R,(CH₃O)₃Si(CH₂)₃C(H)(X)—CO₂R, (CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—CO₂R,(CH₃O)₃Si(CH₂)₄C(H)(X)—CO₂R, (CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—CO₂R,(CH₃O)₃Si(CH₂)₉C(H)(X)—CO₂R, (CH₃O)₂(CH₃)Si(CH₂)₉C(H)(X)—CO₂R,(CH₃O)₃Si(CH₂)₃C(H)(X)—C₆H₅, (CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—C₆H₅,(CH₃O)₃Si(CH₂)₄C(H)(X)—C₆H₅, (CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—C₆H₅(in the above formulas, X is a chlorine, bromine or iodine atom and R isan alkyl, aryl or aralkyl group containing 1 to 20 carbon atoms); etc.

The above-mentioned hydroxyl-group containing organic halide orhalogenated sulfonyl compound is not particularly restricted butincludes, for example, the following:HO—(CH₂)_(n)—OC(O)C(H)(R)(X)wherein X is a chlorine, bromine or iodine atom, R is a hydrogen atom oran alkyl, aryl or aralkyl group containing 1 to 20 carbon atoms and n isan integer of 1 to 20.

The above-mentioned amino-group containing organic halide or halogenatedsulfonyl compound is not particularly restricted but includes, forexample, the following:H₂N—(CH₂)_(n)—OC(O)C(H)(R)(X)wherein X is a chlorine, bromine or iodine atom, R is an alkyl, aryl oraralkyl group containing 1 to 20 carbon atoms and n is an integer of 1to 20.

The above-mentioned epoxy group-containing organic halide or halogenatedsulfonyl compound is not particularly restricted but includes, amongothers, the following:

wherein X is a chlorine, bromine or iodine atom, R is a hydrogen atom oran alkyl, aryl or aralkyl group containing 1 to 20 carbon atoms and n isan integer of 1 to 20.

For obtaining polymers having two or more reactive functional groups ineach molecule, an organic halide or halogenated sulfonyl compound havingtwo or more initiation sites is preferably used as the initiator. Asspecific examples, there may be mentioned the following:

(in the above formulas, C₆H₄ is a phenylene group and X is a chlorine,bromine or iodine atom);

(in the above formulas, R is an alkyl, aryl or aralkyl group containing1 to 20 carbon atoms, n is an integer of 0 to 20 and X is a chlorine,bromine or iodine atom);

(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20);

(in the above formulas, n is an integer of 0 to 20 and X is a chlorine,bromine or iodine atom);

(in the above formulas, X is a chlorine, bromine or iodine atom); etc.

The transition metal complex to be used as the catalyst is notparticularly restricted but preferably is a metal complex containing, asthe central atom, an element of the group 7, 8, 9, 10 or 11 of theperiodic table. More preferred are complexes of zero-valent copper,univalent copper, bivalent ruthenium, bivalent iron or bivalent nickel.Copper complexes are preferred among others. Specific examples of theunivalent copper compound are cuprous chloride, cuprous bromide, cuprousiodide, cuprous cyanide, cuprous oxide and cuprous perchlorate. Whensuch a copper compound is used, a ligand such as 2,2′-bipyridyl or aderivative thereof, 1,10-phenanthroline or a derivative thereof or apolyamine compound such as tetramethylethylenediamine,pentamethyldiethylenetriamine or hexamethyltris(2-aminoethyl)amine isadded for increasing the catalytic activity. Preferred are triaminecompounds. The tristriphenylphosphine complex of bivalent rutheniumchloride (RuCl₂ (PPh₃)₃) is also suited for use as the catalyst. Whensuch a ruthenium compound is used as the catalyst, an aluminum alkoxideis added as an activator. Furthermore, the bivalentiron-bistriphenylphosphine complex (FeCl₂(PPh₃)₂), the bivalentnickel-bistriphenylphosphine complex (NiCl₂(PPh₃)₂), and the bivalentnickel-bistributylphosphine complex (NiBr₂(PBu₃)₂) are also suited foruse as the catalyst.

The vinyl monomer to be used in this polymerization is not particularlyrestricted but includes, among others, (meth)acrylic monomers such as(meth)acrylic acid, methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate, n-butyl(meth)acrylate,isobutyl (meth)acrylate, tert-butyl(meth)acrylate,n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, cyclohexyl(meth)acrylate,n-heptyl(meth)acrylate, n-octyl(meth)acrylate,2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, decyl (meth)acrylate,dodecyl(meth)acrylate, phenyl (meth)acrylate, toluyl(meth)acrylate,benzyl(meth)acrylate, 2-methoxyethyl(meth)acrylate,3-methoxybutyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, stearyl(meth)acrylate,glycidyl(meth)acrylate, 2-aminoethyl(meth)acrylate,γ-(methacryloyloxypropyl)trimethoxysilane, (meth)acrylic acid-ethyleneoxide adducts, trifluoromethylmethyl(meth)acrylate,2-trifluoromethylethyl (meth)acrylate,2-perfluoroethylethyl(meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate,2-perfluoroethyl(meth)acrylate, perfluoromethyl(meth)acrylate,diperfluoromethylmethyl(meth)acrylate,2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate,2-perfluorohexylethyl(meth)acrylate,2-perfluorodecylethyl(meth)acrylate, and2-perfluorohexadecylethyl(meth)acrylate; styrenic monomers such asstyrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonicacid and salts thereof; fluorine-containing vinyl monomers such asperfluoroethylene, perfluoropropylene, and vinylidene fluoride;silicon-containing vinyl monomers such as vinyltrimethoxysilane andvinyltriethoxysilane; maleic anhydride, maleic acid, and maleic acidmonoalkyl esters and dialkyl esters; fumaric acid, and fumaric acidmonoalkyl esters and dialkyl esters; maleimide monomers such asmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide,butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide,stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrilegroup-containing monomers such as acrylonitrile and methacrylonitrile;amide group-containing vinyl monomers such as acrylamide andmethacrylamide; vinyl esters such as vinyl acetate, vinyl propionate,vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenes such asethylene and propylene; conjugated dienes such as butadiene andisoprene; vinyl chloride, vinylidene chloride, allyl chloride, allylalcohol, and the like. These may be used singly or a plurality of themmay be subjected to copolymerization. From the viewpoint of physicalproperties of products, among others, styrenic monomers and(meth)acrylic monomers are preferred among others. Acrylic estermonomers and methacrylic ester monomers are more preferred, and acrylicester monomers are particularly preferred. Butyl acrylate is still morepreferred. In the practice of the present invention, these preferredmonomers may be copolymerized or, further block-copolymerized, withanother monomer and, on that occasion, the content of these preferredmonomers is preferably not less than 40% by weight, more preferably notless than 60% by weight. In the above form of expression, “(meth)acrylicacid”, for instance, means acrylic acid and/or methacrylic acid.

The polymerization can be carried out without using any solvent and canalso be carried out in the presence of various solvents. The solvent isnot particularly restricted in kind but includes, among others,hydrocarbon solvents such as benzene and toluene; ether solvents such asdiethyl ether, tetrahydrofuran, diphenyl ether, anisole, anddimethoxybenzene; halogenated hydrocarbon solvents such as methylenechloride, chloroform, and chlorobenzene; ketone solvents such asacetone, methyl ethyl ketone, and methyl isobutyl ketone; alcoholsolvents such as methanol, ethanol, propanol, isopropanol, n-butylalcohol, and tert-butyl alcohol; nitrile solvents such as acetonitrile,propionitrile, and benzonitrile; ester solvents such as ethyl acetateand butyl acetate; carbonate solvents such as ethylene carbonate andpropylene carbonate; amide solvents such as N,N-dimethylformamide andN,N-dimethylacetamide; and the like. These may be used singly or two ormore of them may be used in admixture. It is also possible to carry outthe polymerization in an emulsion system or in a system using thesupercritical fluid CO₂ as the medium.

The polymerization can be carried out within the temperature range of 0to 200° C., preferably room temperature to 150° C., although thetemperature range is not limited to such range.

Re: Vinyl Polymer

The vinyl polymer according to the present invention is now described indetail.

The vinyl polymer is obtainable by atom transfer radical polymerizationof a vinyl monomer(s). Such vinyl monomer is not particularly restrictedbut any of those already given by way of example can be used. Thosevinyl monomers may be used singly or a plurality of them may becopolymerized. From the viewpoint of physical properties of products,among others, styrenic monomers and (meth)acrylic monomers arepreferred, acrylic ester monomers and methacrylic ester monomers aremore preferred, acrylic ester monomers are particularly preferred, andbutyl acrylate is still further preferred. In the practice of thepresent invention, these preferred monomers may be copolymerized or,further, block copolymerized, with another monomer or other monomersand, on such occasion, these preferred monomers preferably account fornot less than 40% by weight, more preferably not less than 60% byweight.

The molecular weight distribution, namely the ratio between the weightaverage molecular weight and number average molecular weight asdetermined by gel permeation chromatography, of the vinyl polymer is notparticularly restricted but preferably is less than 1.8, preferably notmore than 1.7, more preferably not more than 1.6, still more preferablynot more than 1.5, especially preferably not more than 1.4, mostpreferably not more than 1.3. In the practice of the present invention,the GPC measurement is generally carried out on a polystyrene gel columnusing chloroform as a mobile phase, and the number average molecularweight and the like can be determined on the polystyrene equivalentbasis.

The number average molecular weight of the vinyl polymer is notparticularly restricted but preferably is within the range of 500 to1,000,000, more preferably 1,000 to 100,000. When the molecular weightis too low, the characteristics intrinsic in vinyl polymers can hardlybe manifested and, conversely, when it is excessively high, the polymerbecomes difficult to handle.

The vinyl polymer may have a reactive functional group (s) within themolecule. Where it has a reactive functional group(s) within themolecule, the group(s)_(m)ay occur either on a side chain(s) or at amolecular chain terminus or termini. The reactive functional group isnot particularly restricted but includes, among others, alkenyl,hydroxyl, amino and crosslinkable silyl groups, and polymerizablecarbon-carbon double bonds. The reactive functional group can also beconverted to another appropriate functional group in one or a pluralityof steps. For example, alkenyl group-containing vinyl polymers can besynthesized through conversion of a reactive functional group such as ahydroxyl group in the practice of the present invention as well.

Re: Alkenyl Group-containing Vinyl Polymer

Detailed mention is now made of the alkenyl group-containing vinylpolymer. The alkenyl group-containing vinyl polymer can be used as acomponent in a hydrosilylation-susceptible composition. For example,when subjected to hydrosilylation using a hydrosilyl group-containingcompound as a curing agent, a vinyl polymer having at least one alkenylgroup within the molecule can be crosslinked to give cured products.When subjected to hydrosilylation with a crosslinkable functionalgroup-containing hydrosilane compound, a vinyl polymer having at leastone alkenyl group within the molecule gives a crosslinkable functionalgroup-containing vinyl polymer.

The alkenyl group-containing vinyl polymer can be produced utilizingatom transfer radical polymerization.

In the practice of the present invention, the alkenyl group is notrestricted but preferably is one represented by the general formula (6):H₂C═C(R¹³)—  (6)wherein R¹³ represents a hydrogen atom or an organic group containing 1to 20 carbon atoms.

In the general formula (6), R¹³ is a hydrogen atom or an organic groupcontaining 1 to 20 carbon atoms. The C₁–C₂₀ organic group is notparticularly restricted but preferably is an alkyl group containing 1 to20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or anaralkyl group containing 7 to 20 carbon atoms, typical examples of whichare the following:—(CH₂)_(n)—CH₃, —CH(CH₃)—(CH₂)_(n)—CH₃, —CH(CH₂CH₃)—(CH₂)_(n)—CH₃,—CH(CH₂CH₃)₂, —C(CH₃)₂—(CH₂)_(n)—CH₃, —C(CH₃)(CH₂CH₃)—(CH₂)_(n)—CH₃,—C₆H₅, —C₆H₄(CH₃), —C₆H₃(CH₃)₂, —(CH₂)_(n)—C₆H₅, —(CH₂)_(n)—C₆H₄(CH₃),—(CH₂)_(n)—C₆H₃(CH₃)₂(n being an integer of not less than 0 and the total number of carbonatoms in each group being not more than 20). Among these, a hydrogenatom or a methyl group is more preferred as R¹³.

Further, it is preferred, though not obligatory, that the alkenylgroup(s) in the vinyl polymer be not activated by a carbonyl or alkenylgroup or an aromatic ring, which is conjugated with the carbon-carbondouble bond of the alkenyl group.

The mode of bonding of the alkenyl group to the main chain of thepolymer is not particularly restricted but preferably involvescarbon-carbon bonding, ester bonding, ether bonding, carbonate bonding,amide bonding, urethane bonding or the like.

The alkenyl group(s) is(are) only required to occur within the moleculeof the vinyl polymer. In cases, however, where the cured productsderived from the curable composition of the present invention arerequired to have rubber-like properties, in particular, it is preferredthat at least one of the alkenyl groups occur at a molecular chainterminus so that the molecular weight between crosslinking sites, whichgreatly influences on rubber elasticity, may be designed to be high.More preferably, all alkenyl groups occur at molecular chain termini.

The number of alkenyl groups is not particularly restricted but, forobtaining cured products with a higher degree of crosslinking, it shouldbe, on an average, not less than 1, preferably not less than 1.2, morepreferably not less than 1.5.

Several methods of producing the alkenyl group-containing vinyl polymerare mentioned below in detail, without any purpose of restriction,however.

(A-a) A method comprising subjecting to reaction a compound having, ineach molecule, a polymerizable alkenyl group together with an alkenylgroup of low polymerizability, such as one represented by the generalformula (9) shown below, as a second monomer in synthesizing a vinylpolymer by atom transfer radical polymerization:H₂C═C(R¹⁴)—R¹⁵—R¹⁶—C(R¹⁷)═CH₂  (9)wherein R¹⁴ represents a hydrogen atom or a methyl group, R¹⁵ represents—C(O)O— or an o-, m- or p-phenylene group, R¹⁶ represents a direct bondor a bivalent organic group containing 1 to 20 carbon atoms, which maycontain one or more ether bonds, and R¹⁷ represents a hydrogen atom oran organic group containing 1 to 20 carbon atoms.

In the general formula (9), R¹⁷ is a hydrogen atom or an organic groupcontaining 1 to 20 carbon atoms. The C₁–C₂₀ organic group is notparticularly restricted but preferably is an alkyl group containing 1 to20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or anaralkyl group containing 7 to 20 carbon atoms, typical examples of whichare the following:—(CH₂)_(n)—CH₃, —CH(CH₃)—(CH₂)_(n)—CH₃, —CH(CH₂CH₃)—(CH₂)_(n)—CH₃,—CH(CH₂CH₃)₂, —C(CH₃)₂—(CH₂)_(n)—CH₃, —C(CH₃)(CH₂CH₃)—(CH₂)_(n)—CH₃,—C₆H₅, C₆H₄(CH₃), —C₆H₃(CH₃)₂, —(CH₂)_(n)—C₆H₅, —(CH₂)_(n)—C₆H₄(CH₃),—(CH₂)_(n)—C₆H₃(CH₃)₂(n being an integer of not less than 0 and the total number of carbonatoms in each group being not more than 20).Among these, a hydrogen atom or a methyl group is preferred as R¹⁷.

The time when the compound having, in each molecule, a polymerizablealkenyl group and an alkenyl group of low polymerizability is subjectedto reaction is not particularly restricted but, in particular whenrubber-like properties are expected of the cured products resulting fromcuring of the vinyl polymer, the compound is preferably subjected toreaction as a second monomer at the final stage of the polymerizationreaction or after completion of the reaction of the main monomer(s).

(A-b) A method comprising subjecting to reaction a compound having atleast two alkenyl groups of low polymerizability, for example1,5-hexadiene, 1,7-octadiene or 1,9-decadiene, at the final stage of thepolymerization reaction or after completion of the reaction of the mainmonomer(s) in vinyl polymer synthesis by atom transfer radicalpolymerization.

(A-c) A method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond at a terminus thereof as obtained byatom transfer radical polymerization with one of various alkenylgroup-containing organometallic compounds, for example an organotin suchas allyltributyltin or allyltrioctyltin, for substitution for thehalogen.

(A-d) A method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond at a terminus thereof as obtainableby atom transfer radical polymerization with a stabilized, alkenylgroup-containing carbanion such as one represented by the generalformula (10), for substitution for the halogen:M⁺C⁻(R¹⁸)(R¹⁹)—R²⁰—C(R¹⁷)═CH₂  (10)wherein R¹⁷ is as defined above, R¹⁸ and R¹⁹ each is anelectron-withdrawing group capable of stabilizing the carbanion C⁻ orone of them is such an electron-withdrawing group and the otherrepresents a hydrogen atom, an alkyl group containing 1 to 10 carbonatoms or a phenyl group, R²⁰ represents a direct bond or a bivalentorganic group containing 1 to 10 carbon atoms, which may contain one ormore ether bonds, and M⁺ represents an alkali metal ion or a quaternaryammonium ion.

The electron-withdrawing group R¹⁸ and/or R¹⁹ includes —CO₂R (estergroup), —C(O)R (keto group), —CON(R₂)(amide group), —COSR (thioestergroup), —CN (nitrile group), —NO₂ (nitro group) and so on. Particularlypreferred are —CO₂R, —C(O)R and —CN, however. The substituent R is analkyl group containing 1 to 20 carbon atoms, an aryl group containing 6to 20 carbon atoms or an aralkyl group containing 7 to 20 carbon atomsand preferably is an alkyl group containing 1 to 10 carbon atoms or aphenyl group.

(A-e) A method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond at a terminus thereof, obtainable byatom transfer radical polymerization, with a simple substance metal,such as zinc, or an organometallic compound and then reacting thethus-prepared enolate anion with an alkenyl group-containing,electrophilic compound, such as an alkenyl group-containing compoundhaving a leaving group such as a halogen atom or an acetyl group, analkenyl group-containing carbonyl compound, an alkenyl group-containingisocyanate compound or an alkenyl group-containing acid halide.

(A-f) A method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond at a terminus thereof, obtainable byatom transfer radial polymerization, with an alkenyl group-containingoxy anion or carboxylate anion such as one represented by the generalformula (11) or (12), for substitution for the halogen:H₂C═C(R¹⁷)—R²¹—O⁻M⁺  (11)wherein R¹⁷ and M⁺ are as defined above and R²¹ is a bivalent organicgroup containing 1 to 20 carbon atoms, which may contain one or moreether bonds;H₂C═C(R¹⁷)—R²²—C(O)O⁻M⁺  (12)wherein R¹⁷ and M⁺ are as defined above and R²² is a direct bond or abivalent organic group containing 1 to 20 carbon atoms, which maycontain one or more ether bonds.

Among the methods (A-a) to (A-f), the methods (A-b) and (A-f) arepreferred in view of their easier controllability. The introductionmethods (A-b) and (A-f) are described below in more detail.

Diene Compound Addition Method [Method (A-b)]

The method (A-b) comprises reacting a vinyl polymer obtainable by atomtransfer radical polymerization of a vinyl monomer(s) with a compoundhaving at least two low-polymerizability alkenyl groups (hereinafterreferred to as “diene compound”).

The two alkenyl groups of the diene compound may be the same ordifferent from each other. Each alkenyl group may be a terminal alkenylgroup [CH₂═(R)—R′; R is a hydrogen atom or an organic group containing 1to 20 carbon atoms and R′ is an organic group containing 1 to 20 carbonatoms; R and R′ may be bound together to form a cyclic structure] or aninternal alkenyl group [R′—C(R)═C(R)—R′; R is a hydrogen atom or anorganic group containing 1 to 20 carbon atoms and R′ is an organic groupcontaining 1 to 20 carbon atoms; the two R groups, or the two R′ groups,may be the same or different; any two of the two R and two R′ groups maybe bound together to form a cyclic structure]. A terminal alkenyl groupis preferred, however. R is a hydrogen atom or an organic groupcontaining 1 to 20 carbon atoms. The C₁–C₂₀ organic group is preferablyan alkyl group containing 1 to 20 carbon atoms, an aryl group containing6 to 20 carbon atoms or an aralkyl group containing 7 to 20 carbonatoms. Among these, a hydrogen atom or a methyl group is particularlypreferred as R.

Of the alkenyl groups of the diene compound, at least two alkenyl groupsmay be conjugated.

As specific examples of the diene compound, there may be mentionedisoprene, piperylene, butadiene, myrcene, 1,5-hexadiene, 1,7-octadiene,1,9-decadiene, 4-vinyl-1-cyclohexene and the like. Among them,1,5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

It is also possible to obtain the desired alkenyl-terminated vinylpolymer by carrying out living radical polymerization of a vinylmonomer(s), isolating the resulting polymer from the polymerizationsystem and reacting the thus-isolated polymer with a diene compound inthe manner of radical reaction. According to a more preferred procedure,which is simple and easy to perform, the diene compound is added to thepolymerization reaction system at the final stage of the polymerizationreaction or after completion of the reaction of the main vinylmonomer(s).

It is necessary that the amount of addition of the diene compound beadjusted according to the radical reactivity of each alkenyl group ofthe diene compound. When there is a great difference in reactivitybetween the two alkenyl groups, the amount of the diene compound may beequivalent or in a slight excess relative to the growing polymerizationtermini. When there is little difference in reactivity between the twoalkenyl groups, however, the two alkenyl groups both may react andpolymerization termini may couple together, so that the diene compoundis preferably added in excess, preferably not less than 1.5 times, morepreferably not less than 3 times, most preferably not less than 5 times,relative to the growing polymer termini.

Nucleophilic Substitution Method [Method (A-f)]

The method (A-f) is characterized in that a vinyl polymer having atleast one highly reactive carbon-halogen bond at a terminus thereof,obtainable by atom transfer radical polymerization, is reacted with analkenyl group-containing oxy anion or carboxylate anion for substitutionfor the halogen.

The alkenyl group-containing oxy anion or carboxylate anion is notparticularly restricted but includes, among others, those represented bythe general formula (11) or (12):H₂C═C(R¹⁷)—R²¹—O⁻M⁺  (11)wherein R¹⁷ and M⁺ are as defined above and R²¹ is a bivalent organicgroup containing 1 to 20 carbon atoms, which may contain one or moreether bonds;H₂C═C(R¹⁷)—R²²—C(O)O⁻M⁺  (12)wherein R¹⁷ and M⁺ are as defined above and R²² is a direct bond or abivalent organic group containing 1 to 20 carbon atoms, which maycontain one or more ether bonds.

As specific examples of the oxy anion or carboxylate anion, there may bementioned, among others, salts of alkenyl alcohols such as allylalcohol; salts of allyloxy alcohols such as ethylene glycol monoallylether; salts of alkenyl group-containing phenolic hydroxyl groups suchas allylphenol and allyloxyphenol; salts of alkenyl group-containingcarboxylic acids such as 10-undecylenic acid, 4-pentenoic acid andvinylacetic acid; and so forth.

M⁺ is the counter cation and, as for the species thereof, M⁺ includesalkali metal ions, specifically the lithium ion, sodium ion andpotassium ion, and quaternary ammonium ions. As the quaternary ammoniumions, there may be mentioned the tetramethylammonium ion,tetraethylammonium ion, tetrabenzylammonium ion,trimethyldodecylammonium ion, tetrabutylammonium ion anddimethylpiperidinium ion, etc. The sodium ion and potassium ion arepreferred, however.

The oxy anion or carboxylate anion may be used in excess relative to thehalogen of vinyl polymer, preferably in an amount of 1 to 5 equivalents,more preferably 1 to 2 equivalents, still more preferably 1.0 to 1.2equivalents, relative to the halogen.

The solvent to be used in carrying out this reaction is not particularlyrestricted but preferably is a solvent relatively high in polarity.Thus, for example, there may be mentioned ether solvents such as diethylether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene;halogenated hydrocarbon solvents such as methylene chloride andchloroform; ketone solvents such as acetone, methyl ethyl ketone andmethyl isobutyl ketone; alcohol solvents such as methanol, ethanol,propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrilesolvents such as acetonitrile, propionitrile and benzonitrile; estersolvents such as ethyl acetate and butyl acetate; carbonate solventssuch as ethylene carbonate and propylene carbonate; amide solvents suchas dimethylformamide, dimethylacetamide and hexamethylphosphorictriamide; and sulfoxide solvents such as dimethyl sulfoxide. These maybe used singly or two or more of them may be used in admixture. Amongthem, such polar solvents as acetone, dimethyl sulfoxide,dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide andacetonitrile are preferred. The reaction temperature is not particularlyrestricted but, generally, it is 0 to 150° C., more preferably roomtemperature to 100° C.

An amine, ammonium salt or crown ether, for instance, may be added tothe reaction system as a reaction promoter.

In lieu of an oxy anion or carboxylate anion, an alcohol or carboxylicacid, which is a precursor, may be reacted with a base in the reactionsystem for preparing the corresponding oxy anion or carboxylate anion.

When an ester group exists on side chains or in the main chain of thevinyl polymer, the use of an oxy anion, which is highly nucleophilic,may possibly lead to occurrence of transesterification and, therefore,the use of a carboxylate anion, which is low in nucleophilicity, is morepreferred.

Methods of Converting a Hydroxyl Group to an Alkenyl Group

It is also possible to obtain the vinyl polymer having at least onealkenyl group from a vinyl polymer having at least one hydroxyl group.Utilizable methods include, but are not limited to, the following.

(A-g) A method comprising reacting the hydroxyl group of a vinyl polymerhaving at least one hydroxyl group with a base, such as sodiummethoxide, followed by reaction with an alkenyl group-containing halide,such as allyl chloride.

(A-h) A method comprising reacting the hydroxyl group of a vinyl polymerhaving at least one hydroxyl group with an alkenyl group-containingisocyanate compound, such as allyl isocyanate.

(A-i) A method comprising reacting the hydroxyl group of a vinyl polymerhaving at least one hydroxyl group with an alkenyl group-containing acidhalide, such as (meth)acrylic acid chloride, or 10-undecenoic acidchloride in the presence of a base, such as pyridine.

(A-j) A method comprising reacting the hydroxyl group of a vinyl polymerhaving at least one hydroxyl group with an alkenyl group-containingcarboxylic acid, such as acrylic acid, pentenoic acid or 10-undecenoicacid, in the presence of an acid catalyst.

(A-k) A method comprising reacting a hydroxyl group-containing vinylpolymer with a diisocyanate compound and then reacting the remainedisocyanato group with a compound having both an alkenyl group and ahydroxyl group. The compound having both an alkenyl group and a hydroxylgroup is not particularly restricted but includes, among others, alkenylalcohols such as 10-undecenol, 5-hexenol and allyl alcohol.

The diisocyanate compound is not particularly restricted but may be anyof those known in the art, for example toluylene diisocyanate,4,4′-diphenylmethanediisocyanate, hexamethylene diisocyanate, xylylenediisocyanate, metaxylylene diisocyanate, 1,5-naphthalenediisocyanate,hydrogenated diphenylmethanediisocyanate, hydrogenated toluylenediisocyanate, hydrogenated xylylene diisocyanate,isophoronediisocyanate, and like isocyanate compounds. These may be usedsingly or two or more of them may be used in combination. These may alsobe used in the form of blocked isocyanates.

For making better use of the excellent weatherability, the use ofaromatic ring-free diisocyanate compounds such as hexamethylenediisocyanate and hydrogenated diphenylmethanediisocyanate is preferred.

Methods of Synthesizing Hydroxyl-containing Vinyl Polymers

The method of producing the vinyl polymer having at least one hydroxylgroup, which polymer is to be used in the methods (A-g) to (A-j),includes, but is not limited to, the following, among others.

(B-a) A method comprising subjecting to reaction, as a second monomer, acompound having both a polymerizable alkenyl group and a hydroxyl groupin each molecule, for example one represented by the general formula(15) given below, in synthesizing the vinyl polymer by atom transferradical polymerization:H₂C═C(R¹⁴)—R¹⁵—R¹⁶—OH  (15)wherein R¹⁴, R¹⁵ and R¹⁶ are as defined above.

The time for subjecting to reaction the compound having both apolymerizable alkenyl group and a hydroxyl group in each molecule is notcritical but, in particular in living radical polymerization, whenrubber-like properties are demanded, the compound is preferablysubjected to reaction as a second monomer at the final stage of thepolymerization reaction or after completion of the reaction of the mainmonomer(s).

(B-b) A method comprising subjecting an alkenyl alcohol, such as10-undecenol, 5-hexenol or allyl alcohol, to reaction at the final stageof polymerization reaction or after completion of the reaction of themain monomer(s) in synthesizing the vinyl polymer by atom transferradical polymerization.

(B-c) A method comprising introducing a terminal hydroxyl group(s) byhydrolyzing the halogen atom(s) of a vinyl polymer having at least onehighly reactive carbon-halogen bond at a terminus thereof, obtainable byatom transfer radical polymerization, or reacting such halogen atom(s)with a hydroxyl-containing compound.

(B-d) A method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond at a terminus thereof, obtainable byatom transfer radical polymerization, with a hydroxyl-containingstabilized carbanion, such as one represented by the general formula(16), for substitution for the halogen atom:M⁺C⁻(R¹⁸)(R¹⁹)—R²⁰—OH  (16)wherein R¹⁸, R¹⁹, R²⁰ and M⁺ are as defined above.

The electron-withdrawing groups R¹⁸ and R¹⁹ include —CO₂R (ester group),—C(O)R (keto group), —CON(R²)(amide group), —COSR (thioester group), —CN(nitrile group) and —NO₂ (nitro group), among others. Particularlypreferred are —CO₂R, —C(O)R and —CN, however. The substituent R is analkyl group containing 1 to 20 carbon atoms, an aryl group containing 6to 20 carbon atoms or an aralkyl group containing 7 to 20 carbon atoms,preferably an alkyl group containing 1 to 10 carbon atoms or a phenylgroup.

(B-e) A method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond at a terminus thereof as obtained byatom transfer radical polymerization with a simple substance metal, suchas zinc, or an organometallic compound and then reacting thethus-prepared enolate anion with an aldehyde or ketone.

(B-f) A method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond at a terminus thereof as obtained byatom transfer radical polymerization with a hydroxyl-containing oxyanion or carboxylate anion, such as one represented by the generalformula (17) or (18) given below, for substitution for the halogen atom:HO—R²¹—O⁻M+  (17)wherein R²¹ and M⁺ are as defined above;HO—R²²—C(O)O⁻M⁺  (18)wherein R²² and M⁺ are as defined above.

As for the M⁺, reaction conditions, solvent and so on, those describedwith respect to (A-f) can all appropriately be employed.

(B-g) A method comprising subjecting, as a second monomer, a compoundhaving an alkenyl group of low polymerizability and a hydroxyl group ineach molecule to reaction at the final stage of the polymerizationreaction or after completion of the reaction of the main monomer(s) insynthesizing the vinyl polymer by atom transfer radical polymerization.Such compound is not particularly restricted but may be a compoundrepresented by the general formula (19), for instance:H₂C═C(R¹⁴)—R²¹—OH  (19)wherein R¹⁴ and R²¹ are as defined above.

The compound represented by the above general formula (19) is notparticularly restricted but, in view of ready availability, alkenylalcohols such as 10-undecenol, 5-hexenol and allyl alcohol arepreferred.

Among the synthetic methods (B-a) to (B-g), the methods (B-b) and (B-f)are preferred because of easier controllability.

Re: Halogen Group Treatment Step

In the practice of the present invention, it is also possible to removethe halogen group remained in the vinyl polymer therefrom by carryingout a substitution reaction using a nucleophilic reagent.

The halogen group-containing vinyl polymer is, for example, a vinylpolymer obtainable by carrying out atom transfer radical polymerizationusing an organic halide or halogenated sulfonyl compound as an initiatorand having a terminal structure represented by the general formula (1):—C(R¹)(R²)(X)—  (1)wherein R¹ and R² each represents a group bound to the ethylenicallyunsaturated group of a vinyl monomer and X represents a chlorine,bromine or iodine atom.

The vinyl polymer obtainable by the above-described diene compoundaddition method [method (A-b)] also has such a halogen group. Forexample, whenCH₂═CH—R—CH═CH₂(in which R is a saturated hydrocarbon group containing 1 to 10 carbonatoms) is used, a vinyl polymer having the following molecular terminusis obtained:—C(R¹)(R²)—CH₂—CH(X)—R—CH═CH₂wherein R is a saturated hydrocarbon group containing 1 to 10 carbonatoms.

As the nucleophilic reagent, there may be mentioned those oxy anions andcarbanions having a functional group such as an alkenyl group or ahydroxyl group which have already mentioned hereinabove by way ofexample. When these nucleophilic reagents are used, it is possible tosimultaneously realize halogen group treatment and functional groupintroduction into the vinyl polymer. In cases where only halogen groupelimination is intended and there is no need of particular introductionof a functional group such as an alkenyl or hydroxyl group, however, acarboxylic acid salt such as an acetic acid salt or benzoic acid saltmay be used. Potassium acetate, sodium acetate, potassium benzoate andsodium benzoate are more preferred as the nucleating reagent in view oftheir availability.

As for the nucleophilic substitution reactions, those reactionsmentioned above referring to the nucleophilic substitution method[method (A-f)] may be used as they are.

Re: Adsorption Treatment

The adsorption treatment method is now described in detail.

The adsorption treatment method according to the present invention is amethod of purifying a vinyl polymer by bringing the vinyl polymer intocontact with an adsorbent, which method comprises using an acidadsorbent and a basic adsorbent combinedly. The adsorption treatmentmethod according to the present invention also serves as a method ofpurifying a vinyl polymer for using the vinyl polymer as a component ofa hydrosilylation-susceptible composition.

The transition metal and the ligand added for increasing thepolymerization activity of the metal, which are used in the step ofpolymerization, both become polymer discoloration causing substances.Further, these act as catalyst poisons in the hydrosilylation reaction.The ligand, which is a basic compound, is preferably removed bymeans ofan acidic adsorbent. A basic adsorbent shows high adsorptivity againsttransition metals. Therefore, the both substances can be removedefficiently by using an acidic adsorbent and a basic adsorbentcombinedly and, as compared with the single use of an acidic adsorbentor a basic adsorbent, the transition metal complex used in the step ofpolymerization little remains in the vinyl polymer obtained, and theamount of a hydrosilylation/curing catalyst can be reduced in curing ahydrosilylation-susceptible composition comprising the vinyl polymer.

According to the present invention, an acidic adsorbent and a basicadsorbent are used each as the adsorbent. The term “acidic (or basic)adsorbent” as used herein is defined as “an adsorbent capable ofadsorbing a basic compound (or acidic compound in the case of a basicadsorbent)” or “an adsorbent capable of functioning as a cation (anionin the case of a basic adsorbent) exchanger”.

The adsorbent includes activated carbon, ion exchange resins, othersynthetic resin adsorbents, zeolite and other inorganic adsorbents,among others. All of these can judiciously be used.

Activated carbon is a mostly carbonaceous charcoal and is high inadsorptivity. As for the method of production thereof, wood, brown coal,or peat, for instance, is treated with zinc chloride or phosphoric acid,for instance, as an activator, followed by dry distillation, or charcoalor the like is activated by means of steam. Generally, it has the formof powder or granules, and either form can be used. According to theactivated carbon production process, chemically-activated carbon speciesshow acidity and essentially steam-activated carbon species showbasicity.

Ion exchange resins can be used as synthetic resin adsorbents. Thoseacidic and basic ion exchange resins in general use may be used as theion exchange resins. Chelate type ion exchange resins may also be used.As examples of the functional group of acidic ion exchange resins, theremay be mentioned carboxylic acid and sulfonic acid groups, among others.As examples of the functional group of basic ion exchange resins, theremay be mentioned amino groups, among others. As examples of thefunctional group of chelate type ion exchange resins, there may bementioned iminodiacetic acid and polyamine groups, among others.

Inorganic adsorbents generally comprise a solid acid or solid base, andparticles thereof have a porous structure and, therefore, they are veryhigh in adsorptivity. One of the characteristic features thereof is tatthey can be used at low temperatures to elevated temperatures. While theinorganic adsorbents are not particularly restricted, representativespecies comprise, either singly or in combination, aluminum, magnesium,silicon and/or the like as main component(s). Examples are silicondioxide; magnesium oxide; silica gel; silica-alumina, aluminum silicate;magnesium silicate; activated alumina, aluminum hydroxide; acidic terraalba, activated terra alba, and like clay adsorbents; sodium aluminumsilicate and like zeolite adsorbents collectively called hydratealuminosilicate minerals; dawsonite compounds; and hydrotalcites, amongothers.

Zeolites include natural products and synthetic products. Either of themmay be used.

Silicon dioxide includes crystalline, amorphous, noncrystalline,glass-like, synthetic and natural species. Any of them can be used hereif occurring in a powder form. Thus, silicon dioxide includes, but isnot limited to, silicic acid products derived from clay mineralsobtainable by acid treatment of activated terra alba, and syntheticsilicic acid species such as Carplex BS304, Carplex BS304F, Carplex #67and Carplex #80 (all available from Shionogi & Co., Ltd.).

Aluminum silicates are derived from silicic acid by partial substitutionof aluminum atoms for silicon atoms, and known species include pumice,fly ash, kaolin, bentonite, activated terra alba, and diatomaceousearth, among others. Synthetic aluminum silicates are large in specificsurface area and high in adsorptivity. Synthetic aluminum silicatesinclude, but are not limited to, Kyowaad 700 series products (productsof Kyowa Chemical).

Hydrotalcites include hydrate hydroxides of a bivalent metal (e.g. Mg²⁺,Mn2+, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺) and a trivalent metal (e.g. Al³⁺,Fe³⁺, Cr³⁺, Co³⁺, In³⁺) and derivatives of such hydroxides as obtainedby partial exchange of anions such as halogen ions, NO₃ ⁻, CO₃ ²⁻, SO₄²⁻, Fe(CN)₆ ³⁻, CH₃CO₂ ⁻, oxalic ion, and salicylic acid ion forhydroxyl groups thereof. Species preferred among these include, but arenot limited to, hydrotalcites in which the bivalent metal is Mg²⁺, thetrivalent metal is Al³⁺ and hydroxyl groups thereof have partly beenexchanged for CO₃ ²⁻ groups, for example synthetic products such asKyowaad 500 series and Kyowaad 1000 series products (all being productsof Kyowa Chemical). Those adsorbents obtained by calcining suchhydrotalcites are also suited for use. Species preferred among theminclude, but are not limited to, MgO—Al₂O₃-based solid solutionsobtainable by calcining those hydrotalcites in which the bivalent metalis Mg²⁺ and the trivalent metal is Al³⁺, for example Kyowaad 2000(product of Kyowa Chemical). In accordance with the present invention,such calcined hydrotalcites are also classified as hydrotalcites.

An adsorbent comprising both a solid acid and a solid base may be usedinstead of the combined use of an acidic adsorbent and a basicadsorbent. As such adsorbent, there may be mentioned magnesiumsilicates. Magnesium silicates are composed of a solid acid and a solidbase and can adsorb both acids and bases. Such magnesium silicatesinclude, but are not limited to, Kyowaad 600s (2MgO.6SiO₂.xH₂O; productof Kyowa Chemical) and Mizukalife P-1G (product of Mizusawa IndustrialChemicals), among others. Kyowaad 600s is capable of adsorbing bothacids and bases and therefore can be classified as an acidic adsorbentand at the same time as a basic adsorbent whereas Mizukalife P-1G ishigher in adsorptivity for bases and therefore classified as an acidicadsorbent.

Aluminum hydroxide is amphoteric and capable of adsorbing bases undercertain conditions. However, it is an adsorbent mainly for acids, henceis classified as a basic adsorbent.

Al(OH)₃.NaHCO₃, which is also known as dawsonite, is classified as abasic adsorbent.

Thus, acidic inorganic adsorbents include, amongothers, acid terra alba,activated terra alba, aluminum silicates, silica gel, and the like.Basic inorganic adsorbents include, among others, magnesium oxide,activated alumina, zeolite adsorbents collectively called hydratealuminosilicate minerals, such as sodium aluminum silicate, andhydrotalcites.

Among those mentioned above, inorganic adsorbents are preferred as theadsorbent to be used in adsorption treatment of the vinyl polymer.Preferred among them as acidic adsorbents are acidic terra alba,activated terra alba and aluminum silicates. Activated terra alba andaluminum silicates are more preferred, and aluminum silicates are mostpreferred. Preferred as basic adsorbents are activated alumina, zeoliteadsorbents collectively called hydrate aluminosilicate minerals, such assodium aluminum silicate, and hydrotalcites. Activated alumina andhydrotalcites are more preferred, and hydrotalcites are most preferred.

The adsorbents may be used singly or two or more of them may be used inadmixture.

The vinyl polymer produced by atom transfer radical polymerization canbe purified by bringing the same into contact with an acidic adsorbentand a basic adsorbent. The polymer may be contacted with a mixture of anacidic adsorbent and a basic adsorbent or with the respective adsorbentsin separate steps. For example, when a substitution reaction is carriedout using a nucleophilic reagent in such a halogen group treatment stepas mentioned below, or when no solvent is used or dilution is made witha solvent, it is possible to bring the polymer into contact with one ofan acidic adsorbent and a basic adsorbent in such step and with theother in another step.

When a substitution reaction is carried out using a nucleophilic reagentin the halogen group treatment step, a halide corresponding to thecounter cation is formed. For example, when a carboxylic acid alkalimetal salt is used as the nucleophilic reagent, an alkali metal halideis formed. In such case, the vinyl polymer after nucleophilicsubstitution reaction can be contacted with an adsorbent(s) withoutseparating the above halide, namely in the presence thereof. Thereby,the halide removal step can be omitted.

The vinyl polymer produced by atom transfer radical polymerization maybe brought into contact with an adsorbent(s) without using any solvent,or after dilution with a solvent, or after distilling off the solvent byconcentrating the reaction mixture. From the solvent recyclingviewpoint, among others, it is preferred that the vinyl polymerconcentration is as high as possible, and a solvent-free state is mostpreferred. When, however, the vinyl polymer is high in viscosity andthus difficult to handle, for instance, the polymer may be contactedwith the adsorbent(s) in a solution state resulting from dilution with asmall amount of a solvent. In that case, the concentration of the vinylpolymer is preferably not less than 60% by weight, more preferably notless than 70% by weight, still more preferably not less than 80% byweight, most preferably not less than 90% by weight. The dilutionsolvent may be any of those in general use.

The adsorption treatment temperature is not particularly restricted but,recommendably, the treatment is carried out generally at 0° C. to 200°C., preferably at room temperature to 180° C. When no solvent is used,the treatment is preferably carried out at a higher temperature,generally within the range of 0° C. to 250° C., preferably roomtemperature to 200° C., more preferably 100° C. to 180° C.

In view of the economy and operability, it is necessary that theadsorbent be used in an amount within the range of 0.01 to 10 parts byweight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10parts by weight, still more preferably 0.5 to 5 parts by weight, mostpreferably 0.5 to 2 parts by weight, per 100 parts by weight of thevinyl polymer.

The solid-liquid contacting between the adsorbent(s) and the polymer orpolymer solution can be effected in various modes of embodiment. Thus,in addition to the batchwise procedure in which the operations ofstirring/mixing and solid-liquid separation are carried out batchwise,the fixed bed system in which the polymer solution is passed through anadsorbent packed in a vessel, the moving bed system in which the polymersolution is passed through a moving adsorbent bed, and the fluidized bedsystem in which the adsorbent is fluidized by means of the liquid phaseto thereby effect the adsorption, among others, can also be utilized. Inaddition to mixing and dispersion by stirring, it is further possible toemploy, if necessary, various procedures for improving the dispersionefficiency, for example shaking of the vessel, utilization of ultrasonicwaves, and so on.

After contacting of the polymer or polymer solution with theadsorbent(s), the adsorbent(s) is(are) removed by such a method asfiltration, centrifugation or sedimentation, if necessary followed bydilution and/or washing with water, whereby the desired clear polymersolution can be obtained.

While it is necessary only that the final product vinyl polymer issubjected to the adsorption treatment, that treatment may also beapplied to the intermediate for the production of the vinyl polymer. Inthe case of an alkenyl group-containing vinyl polymer obtained by atomtransfer radical polymerization, for instance, the polymer itself aswell as vinyl polymers to serve as intermediates for the production ofthat polymer, for example a highly reactive carbon-halogenbond-containing vinyl polymer and a hydroxyl group-containing vinylpolymer, can be subjected to that adsorption treatment.

Hydrosilylation Reaction-susceptible Composition

The hydrosilylation reaction-susceptible composition according to thepresent invention contains the vinyl polymer after the above-mentionedadsorption treatment.

The hydrosilylation reaction-susceptible composition of the presentinvention is, for example, a hydrosilylation reaction-susceptiblecomposition comprising (A) a vinyl polymer and (B) a hydrosilylgroup-containing compound.

The A component vinyl polymer is a vinyl polymer obtainable by utilizingthe above-described atom transfer radical polymerization, preferably avinyl polymer having an alkenyl group(s) within the molecule thereof,and may be any of those mentioned hereinabove. The B componenthydrosilyl group-containing compound is not particularly restricted butmay be any of various species. Thus, it includes, among others,compounds having at least 1.1 hydrosilyl groups within the molecule, andhydrosilane compounds having a crosslinkable silyl group(s) as well.Specific hydrosilylation reaction-susceptible compositions are shownbelow.

<Hydrosilylation Reaction-susceptible Composition (1)>

When the B component is a compound having at least 1.1 hydrosilyl groupswithin the molecule, the composition gives cured products as a result ofhydrosilylation. Thus, the hydrosilylation reaction-susceptiblecomposition is a curable composition (curable composition (1)).

Such compound having at least 1.1 hydrosilyl groups within the moleculeis not particularly restricted but include, among others, linearpolysiloxanes represented by the general formula (22) or (23):R²³ ₃SiO—[Si(R²³)₂O]_(a)[Si(H)(R²⁴)O]_(b)—[Si(R²⁴)(R²⁵)O]_(c)—SiR²³₃  (22)HR²³ ₂SiO—[Si(R²³)₂O]_(a)—[Si(H)(R²⁴)O]_(b)—[Si(R²⁴)(R²⁵)O]_(c)—SiR²³₂H  (23)wherein R²³ and R²⁴ each represents an alkyl group containing 1 to 6carbon atoms or a phenyl group, R²⁵ represents an alkyl, phenyl oraralkyl group containing 1 to 10 carbon atoms, and a, b and c eachrepresents an integer satisfying the relation 0≦a≦100, 2≦b≦100 and0≦c≦100; cyclic siloxanes represented by the general formula (24):

wherein R²⁶ and R²⁷ each represents an alkyl group containing 1 to 6carbon atoms or a phenyl group, R²⁸ represents an alkyl, phenyl oraralkyl group containing 1 to 10 carbon atoms and, when there are two ormore R²⁶ and/or R²⁷ groups, they may be the same or different; and d, eand f each represents an integer satisfying the relation 0≦d≦8, 2≦e≦10or 0≦f≦8 provided that the relation 3≦d+e+f≦10 should be satisfied); andso forth.

These may be used singly or two or more of them may be used inadmixture. Among these siloxanes, phenyl-containing linear siloxanesrepresented by the general formula (25) or (26) shown below and cyclicsiloxanes represented by the general formula (27) or (28) given beloware preferred from the viewpoint of compatibility with (meth)acrylicpolymers.(CH₃)₃SiO—[Si(H)(CH₃)O]_(g)—[Si(C₆H₅)₂O]_(h)—Si(CH₃)₃  (25)(CH₃)₃SiO—[Si(H)(CH₃)O]_(g)—[Si(CH₃){CH₂C(H)(R″)C₆H₅}O)_(h)—Si(CH₃)₃  (26)(in the above formulas, R″ represents a hydrogen atom or a methyl group,g and h each represents an integer satisfying the relation 2≦g≦100 or0≦h≦100; and C₆H₅ represents a phenyl group.)

(in the above formulas, R²⁹ represents a hydrogen atom or a methylgroup, i and j each represents an integer satisfying the relation 2≦i≦10or 0≦j≦8 with the condition 3≦i+j≦10; and C₆H₅ represents a phenylgroup.)

Further usable as the compound containing at least 1.1 hydrosilyl groupsin the B component are compounds obtainable by subjecting alow-molecular-weight compound having two or more alkenyl groups withinthe molecule and a hydrosilyl group-containing compound represented byany of the general formulas (22) to (28) to addition reaction in amanner such that the hydrosilyl group partially remains even afterreaction. Various compounds can be used as the compound having two ormore alkenyl groups within the molecule. Examples are hydrocarboncompounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene and 1,9-decadiene, ether compounds such asO,O′-diallylbisphenol A and 3,3′-diallylbisphenol A, ester compoundssuch as diallyl phthalate, diallyl isophthalate, triallyl trimellitateand tetraallyl pyromellitate, and carbonate compounds such as diethyleneglycol diallyl carbonate.

The above compounds can be obtained by slowly adding dropwise the abovealkenyl group-containing compound to an excess of the hydrosilylgroup-containing compound represented by one of the general formulas(22) to (28) shown above in the presence of a hydrosilylation catalyst.Among such compounds, the following ones are preferred in view of theready availability of raw materials, the ease of removal of the siloxaneused in excess and, further, the compatibility with the vinyl polymer:

(n being an integer of 2 to 4 and m being an integer of 5 to 10).

The A component vinyl polymer and the B component hydrosilylgroup-containing compound can be blended in an arbitrary mixing ratio.From the curability viewpoint, however, the mole ration between thealkenyl and hydrosilyl groups is preferably within the range of 5 to0.2, more preferably 2.5 to 0.4. When the mole ratio is about 5, thecuring tends to become insufficient and give sticky cured products,which is low in strength. When the mole ratio is smaller than 0.2, theactive hydrosilyl group tends to remain in large amounts in the curedproducts even after curing, readily causing the formation of cracks andvoids, and thus tends to make it difficult to obtain uniform and strongcured products.

The curing reaction between the A component vinyl polymer and the Bcomponent hydrosilyl group-containing compound proceeds when the twocomponents are mixed up and heated. For increasing the rate of reaction,a hydrosilylation catalyst can be added. Such hydrosilylation catalystis not particularly restricted but may be a radical initiator such as anorganic peroxide or azo compound, or a transition metal catalyst, forinstance.

The radical initiator is not particularly restricted but includes, amongothers, dialkyl peroxides such as di-t-butyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, dicumyl peroxide, t-butylcumyl peroxide and α,α′-bis(t-butylperoxy)isopropylbenzene, diacylperoxides such as benzoyl peroxide, p-chlorobenzoyl peroxide,m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide and lauroylperoxide, peresters such as t-butyl perbenzoate, peroxydicarbonates suchas diisopropyl peroxydicarbonate and di-2-ethylhexyl peroxydicarbonate,and peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane and1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane.

The transition metal catalyst is not particularly restricted, either,but includes, among others, simple substance platinum, solid platinumdispersed on/in a carrier such as alumina, silica or carbon black,chloroplatinic acid, complexes of chloroplatinic acid with alcohol,aldehyde, ketone, or the like compound, platinum-olefin complexes, andplatinum(0)-divinyltetramethyldisiloxane complex. As other catalyststhan platinum compounds, there may be mentioned RhCl(PPh₃)₃, RhCl₃,RuCl₃, IrCl₃, FeCl₃, AlCl₃, PdCl₂.H₂O, NiCl₂ and TiCl₄, among others.These catalysts may be used singly or two or more of them may be used incombination. The amount of the catalyst is not particularly restrictedbut recommendably is within the range of 10⁻¹ to 10⁻⁸ mole, preferablywithin the range of 10⁻³ to 10⁻⁶ mole, per mole of the alkenyl group inthe component (A). When it is smaller than 10⁻⁸ mole, the curing tendsto proceed only to a satisfactory extent. Since the hydrosilylationcatalyst is generally expensive and corrosive and may cause, in somecases, generation of a large amount of hydrogen gas, hence foaming ofcured products, it is preferred that an amount thereof exceeding 10⁻¹mole be not used.

The curing temperature is not particularly restricted but it isrecommended that the curing be carried out generally at 0° C. to 200°C., preferably 30° C. to 150° C., more preferably 80° C. to 150° C. Inthis way, the curable composition can be cured in a short period oftime.

<Hydrosilylation Reaction-susceptible Composition (2)>

A hydrosilane compound having a crosslinkable silyl group additionallymay be used as the hydrosilyl group-containing compound of the Bcomponent.

The crosslinkable silyl group-containing hydrosilane compound is notparticularly restricted but includes, as typical examples, compoundsrepresented by the general formula (29)H—[Si(R¹¹)_(2−b)(Y)_(b)O]_(m)—Si(R¹²)_(3−a)(Y)_(a)  (29)wherein R¹¹ and R¹² each represents an alkyl group containing 1 to 20carbon atoms, an aryl group containing 6 to 20 carbon atoms, an aralkylgroup containing 7 to 20 carbon atoms or a triorganosiloxy grouprepresented by (R′)₃SiO— (in which R′ is a univalent hydrocarbon groupcontaining 1 to 20 carbon atoms and the three R′ groups may be the sameor different) and, when there are two or more R¹¹ or R¹² groups, theymay be the same or different; Y represents a hydroxyl group or ahydrolyzable group and, when there are two or more Y groups, they may bethe same or different; a represents 0, 1, 2 or 3, b represents 0, 1 or 2and m is an integer of 0 to 19, provided that the relation a+mb≧1 shouldbe satisfied.

As the hydrolyzable group, there may be mentioned, among others, ahydrogen atom and those groups which are in general use, for examplealkoxy, acyloxy, ketoximate, amino, amido, aminoxy, mercapto andalkenyloxy groups. Among them, alkoxy, amido and aminoxy groups arepreferred. In view of mild hydrolyzability and ease of handling, alkoxygroups are particularly preferred.

One to three hydrolyzable groups and/or hydroxy groups can be bound toeach silicon atom, and it is preferred that (a+Σb) is within the rangeof 1 to 5. When there are two or more hydrolyzable groups or hydroxylgroups bound in one crosslinkable silyl group, they may be the same ordifferent. The number of silicon atoms forming the crosslinkable silylgroup is not less than 1 and, in the case of silicon atoms connected bysiloxane or like bonding, it is preferably not more than 20.

Particularly preferred among those hydrosilane compounds in view ofready availability are crosslinkable group-containing compoundsrepresented by the general formula (30):H—Si(R¹²)_(3−a)(Y)_(a)  (30)wherein R¹², Y and a are as defined above.

When a hydrosilylation reaction-susceptible composition in which theabove-described hydrosilane compound is used as the B componentundergoes hydrosilylation, a vinyl polymer having a crosslinkable silylgroup(s) within the molecule can be obtained.

Such vinyl polymer having at least 1.1 crosslinkable Silyl groups ineach molecule can be crosslinked to give cured products. The vinylpolymer having at least 1.1 crosslinkable silyl groups as obtained bythe above process as well as a curable composition (curable composition(2)) comprising such vinyl polymer also constitutes an aspect of thepresent invention.

As the crosslinkable silyl groups to be used in the practice of thepresent invention, there maybe mentioned groups represented by thegeneral formula (31):—[Si(R¹¹)_(2−b)(Y)_(b)O]_(m)—Si(R¹²)_(3−a)(Y)_(a)  (31)wherein, R¹¹ and R¹² each is an alkyl group containing 1 to 20 carbonatoms, an aryl group containing 6 to 20 carbon atoms, an aralkyl groupcontaining 7 to 20 carbon atoms or a triorganosiloxy group representedby (R′)₃SiO— (in which R′ is a univalent hydrocarbon group containing 1to 20 carbon atoms and the three R′ groups may be the same or different)and, when there are two or more R¹¹ or R¹² groups, they may be the sameor different; Y represents a hydroxyl group or a hydrolyzable group and,when there are two or more Y groups, they may be the same or different;a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and m is an integerof 0 to 19, provided that the relation a+mb≧1 should be satisfied.

As the hydrolyzable group, there may be mentioned, among others, ahydrogen atom and those groups which are in general use, for examplealkoxy, acyloxy, ketoximate, amino, amido, aminoxy, mercapto andalkenyloxy groups. Among them, alkoxy, amido and aminoxy groups arepreferred. In view of mild hydrolyzability and ease of handling, alkoxygroups are particularly preferred.

One to three hydrolyzable groups and/or hydroxyl groups can be bound toeach silicon atom, and it is preferred that (a+Σb) is within the rangeof 1 to 5. When there are two or more hydrolyzable groups or hydroxylgroups bound in one crosslinkable silyl group, they may be the same ordifferent. The number of silicon atoms forming the crosslinkable silylgroup is not less than 1 and, in the case of silicon atoms connected bysiloxane or like bonding, it is preferably not more than 20. Especiallypreferred are crosslinkable silyl groups represented by the generalformula (32):—Si(R¹²)_(3−a)(Y)_(a)  (32)wherein R¹², Y and a are as defined above, because of their readyavailability.

When the cured products resulting from curing of the crosslinkable silylgroup-containing vinyl polymer according to the present invention arerequired to have rubber-like properties, in particular, it is preferredthat at least one of the crosslinkable silyl groups occur at a molecularchain terminus in order that the molecular weight between crosslinkingsites, which greatly influences on the rubber elasticity, may bedesigned to be high. More preferably, the polymer has all functionalgroups at molecular chain termini.

The mixing ratio between the A component vinyl polymer and thecrosslinkable silyl group-containing hydrosilane compound as the Bcomponent is not particularly restricted but it is preferred that thehydrosilyl group content be at least equivalent to the alkenyl groupcontent.

For causing the hydrosilylation reaction to proceed more rapidly, ahydrosilylation catalyst may be added. Such hydrosilylation catalyst maybe any of those already mentioned hereinabove by way of example.

The reaction temperature is not particularly restricted but generally is0° C. to 200° C., preferably 30° C. to 150° C., more preferably 80° C.to 150° C.

In curing the curable composition (2), a condensation catalyst may beused or may not be used. Thus, use as the condensation catalyst may bemade, according to need, of one or more of the following: titanates suchas tetrabutyl titanate and tetrapropyl titanate; organotin compoundssuch as dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltinmaleate, dibutyltin diacetate, dibutyltin dimethoxide, stannousoctylate, and stannous naphthenate; lead octylate; amine compounds suchas butylamine, octylamine, dibutylamine, monoethanolamine,diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, octylamine, cyclohexylamine,benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine,and 1,3-diazabicyclo[5.4.6]undecene-7, or salts of these amine compoundswith carboxylic acids; amine compound-organotin compound reactionproducts and mixtures, for example a laurylamine-stannous octylatereaction product or mixture; low-molecular-weight polyamide resinsobtainable from a polyamine in excess and a polybasic acid; reactionproducts from a polyamine in excess and an epoxy compound; aminogroup-containing silane coupling agents such asγ-aminopropyltrimethoxysilane andN-(β-aminoethyl)aminopropylmethyldimethoxysilane; and other knownsilanol condensation catalysts. The amount of addition is preferably 0to 10% by weight relative to the crosslinkable silyl group-terminatedvinyl polymer. When the hydrolyzable group Y is an alkoxy group, thecorresponding polymer, when used alone, shows a slow rate of curing, sothat a curing catalyst is preferably used.

<Curable Composition>

In the above curable composition (1) and curable composition (2), theremaybe incorporate various additives for physical property modification,for example flame retardants, antioxidants, fillers, plasticizers,physical property modifiers, reactive diluents, adhesiveness-providingagents, storage stability-improving agents, solvents, radicalinhibitors, metal deactivators, antiozonants, phosphorus-containingperoxide decomposing agents, lubricants, pigments, foaming, agents,photocurable resins and the like. These additives may be used singly ortwo or more of them may be used in combination.

Since the vinyl polymer is excellent in nature in durability, hence theuse of an antioxidant is not always necessary. However, any of thoseantioxidants, ultraviolet absorbers, light stabilizers and the likewhich are known in the art can be used each in an appropriate amount.

<Fillers>

The filler which can be incorporated is not particularly restricted butincludes, among others, finely powdered silica, calcium carbonate, talc,titanium oxide, diatomaceous earth, barium sulfate, carbon black,surface-treated finely divided calcium carbonate, calcined clay, clayand activated zinc white and like reinforcing fillers, which are usedfor providing strength and other physical features. These reinforcingfillers may be used singly or two or more of them may be used incombination. Among them, finely powdered silica species are preferred.Thus, hydrous silica obtainable by the wet process or the like, anddryprocess silica obtainable by the dryprocess or the like can be used,among others. Among them, anhydrous silica is particularly preferredsince when the composition has high moisture content, side reactions andthe like may possibly occur in the curing reaction step. Furthermore,hydrophobically surface-treated anhydrous silica is particularlypreferred since such can readily provide flowability suited for molding.In addition, fillers not so outstanding in reinforcing ability may alsobe used for extension or physical property modification.

<Plasticizer>

The plasticizer which can be incorporated is not particularly restrictedbut, according to the purpose of addition, for example adjustment ofphysical properties and/or adjustment of other properties, use can bemade of one or a mixture of two or more of phthalates such as dibutylphthalate, diheptyl phtbalate, di(2-ethylhexyl) phthalate and butylbeuzyl phtbalate; nonaromatic dibasic carboxylates such as dioctyladipate, dioctyl sebacate, dibutyl sebacate and isodecyl succinate;fatty acid esters such as butyl oleate and methyl acetyiricinolate;polyalkylene glycol esters such as diethylene glycol dibeuzoate,triethylene glycol dibenzoate and pentaerytbritol esters; phosphatessuch as tricresyl phosphate and tributyl phosphate; trimellitates;polystyrenes such as polystyrene and poly α-methylstyrene;polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrilecopolymers, polychloroprene; chlorinated paraffins; hydrocarbon oilssuch as alkyldiphenyls and partially hydrogenated terphenyl; processoils; polyethers such as polyethylene glycol, polypropylene glycol,polytetramethylene glycol and like polyether polyols and derivatives ofthese polyether polyols as resulting from conversion of hydroxyl groupsthereof to ester, ether and/or like groups; epoxy plasticizers such asepoxidized soybean oil and benzyl epoxystearate; polyester plasticizersobtainable from a dibasic acid, such as sebacic acid, adipic acid,azelaic acid or phthalic acid, and a dihydric alcohol, such as ethyleneglycol, diethylene glycol, triethylene glycol, propylene glycol ordipropylene glycol; and vinyl polymers obtainable by polymerizing avinyl monomer(s) by various methods, typically acrylic plasticizers,among others, although these are not always necessary. It is alsopossible to incorporate these plasticizers in the process of polymerproduction.

<Storage Stability-improving Agent>

The storage stability-improving agent which can be incorporated is notparticularly restricted but may by any one that can prevent theviscosity of the resulting composition from increasing during storageand prevent the curing rate from markedly changing after storage. Forexample, there may be mentioned benzothiazole and dimethyl maleate.

<Solvent>

As examples of the solvent which can be incorporated, there may bementioned aromatic hydrocarbon solvents such as toluene and xylene,ester solvents such as ethyl acetate, butyl acetate, amyl acetate andceliosolve acetate, and ketone solvents such as methyl ethyl ketone,methyl isobutyl ketone and diisobutyl ketone, among others. Thesesolvents may also be used in the step of polymer production.

<Adhesiveness-providing Agent>

The adhesiveness-providing agent to be incorporated is not particularlyrestricted but may be any of those capable of providing the curedproducts with adhesive properties. A crosslinkable silylgroup-containing compound is preferred, however, and a silane couplingagent is more preferred. As specific examples thereof, there may bementioned alkylalkoxysilanes such as methyltrimethoxysilane,dimethyldimethoxysilane, trimethylmethoxysilane andn-propyltrimethoxysilane; alkylisopropenoxysilanes such asdimethyldiisopropenoxysilane and methyltriisopropenoxysilane; vinyl typeunsaturated group-containing silanes such as vinyltrimethoxysilane,vinyldimethylmethoxysilane, vinyltriethoxysilane,γ-methacryloyloxypropylmethyldimethoxysilane andγ-acryloyloxypropylmethyltriethoxysilane; silicone vanishes;polysiloxanes and so forth.

Among them, silane coupling agents having, within the molecule, both acrosslinkable silyl group and an organic group having an atom(s) otherthan carbon and hydrogen atoms, for example an epoxy group,(meth)acrylic group, isocyanato group, isocyanurate group, carbamategroup, amino group, mercapto group, carboxyl group or halogen group, arepreferred. As specific examples thereof, there may be mentioned areepoxy group-containing alkoxysilanes such asγ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane,γ-glycidoxypropylmethyldiisopropenoxysilane and like epoxygroup-containing silanes; (meth)acrylic group-containing alkoxysilanessuch as γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane,γ-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane,methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane,acryloxymethyltriethoxysilane and like (meth)acryl group-containingsilanes; isocyanato group-containing alkoxysilanes such asγ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane,γ-isocyanatopropylmethyldiethoxysilane,γ-isocyanatopropylmethyldimethoxysilane and like isocyanatogroup-containing silanes; isocyanurate group-containing alkoxysilanessuch as tris(trimethoxysilyl)isocyanurate and like isocyanurate silanes;carbamate group-containing alkoxysilanes; amino group-containingalkoxysilanes such as γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-aminopropylmethyldiethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane,N-(β-aminoethyl)-γ-aminopropyltriethoxysilane,N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane,γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane,N-vinylbenzyl-γ-aminopropyltriethoxysilane and like aminogroup-containing silanes; mercapto group-containing alkoxysilanes suchas γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane and like mercapto group-containingsilanes; carboxyl group-containing alkxoysilanes such asβ-carboxyethyltriethoxysilane,β-carboxyethylphenylbis(2-methoxyethoxy)silane,N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane and likecarboxysilanes; halogen group-containing alkoxysilanes such asγ-chloropropyltrimethoxysilane and like halogen-containing silanes.These may be used singly or two or more of them may be used incombination.

Also usable as the silane coupling agent are modified derivatives ofthese, for example amino-modified silyl polymers, silylated aminopolymers, unsaturated aminosilane complexes, phenylamino-long chainalkylsilanes, aminosilylated silicones, and silylated polyesters.

Further, among these, alkoxysilanes having an epoxy group or (meth)acrylgroup within the molecule are preferred from the curability andadhesiveness viewpoint.

For further improving the adhesiveness, a crosslinkable silyl groupcondensation catalyst can be used in combination with the above adhesiveproperty-providing agent. As the crosslinkable silyl group condensationcatalyst, there may be mentioned organotin compounds such as dibutyltindilaurate, dibutyltin diacetylacetonate, dibutyltin dimethoxide andstannous octylate, organoaluminum compounds such as aluminumacetylacetonate, and organotitanium compounds such astetraisopropoxytitanium and tetrabutoxytitanium, among others.

Other specific examples than silane coupling agents include, but are notparticularly limited to, epoxy resins, phenol resins, sulfur, alkyltitanates, aromatic polyisocyanates and the like.

The above adhesive property providing agent is used preferably in anamount of 0.01 to 20 parts by weight per 100 parts by weight of thevinyl polymer. At a level below 0.01 parts by weight, the adhesivenessimproving effect tends to become poor and, at levels exceeding 20 partsby weight, the physical properties of the cured products may beadversely affected. The range of 0.1 to 10 parts by weight is preferred,and the range of 0.5 to 5 parts by weight is more preferred.

The adhesive property-providing agents specifically mentioned above maybe used singly or two or more of them may be used in admixture. Byadding these adhesive property-providing agents, it is possible toimprove the adhesion to adherends.

<Method of Molding>

In using the curable composition of the present invention in the form ofmoldings, the method of molding is not particularly restricted but maybe any of various molding methods in general use. For example, there maybe mentioned cast molding, compression molding, transfer molding,injection molding, extrusion molding, rotational molding, blow molding,thermal molding, etc. In particular, injection molding is preferred inview of the possibility of automation and continuous operation, and goodproductivity. For use as gaskets, for instance, both the wet typeprocess, in which the curable composition interposed between the matingfaces of flanges or the like is compressed from both sides in theuncured condition, followed by curing, and the dry type one, in whichthe composition is first cured and then compressed, can be used.

<Uses>

The curable composition of the present invention can be used in variousfields of application which include, but are not limited to, sealingmaterials, for example elastic sealing materials for building andconstruction and sealing materials for multilayer glass, electric andelectronic part materials such as solar cell back sealers, electricinsulating materials such as wire/cable insulating sheath, pressuresensitive adhesive materials, adhesives, elastic adhesives, paints,powder paints, coating compositions, foamed bodies, potting materialsfor electric and electronic use, films, gaskets, casting materials,artificial marble, various molding materials, and rust proof andwaterproof sealants for end faces (cut sections) of net glass ormultilayer glass.

Further, moldings showing rubber elasticity as obtained from the curablecomposition of the present invention can be widely used as gaskets andpacking materials. For example, they can be used as body parts in theautomobile field, sealants for securing air tightness, vibration dampermaterials for glass, and vibration damper materials for automotivebodies, in particular, window sealing gaskets and door glass gaskets.They can be used as chassis parts, such as engine and suspension rubbersfor vibration-damping and sound-insulating materials, in particularengine mount rubbers. As for engine parts, they can be used in producinghoses for cooling, fuel feeding and exhaust control, or as engine oilsealants and so on. They can be used also as or in exhaust gas cleanerparts and brake parts. In the field of household electric appliances,they can be used as packing materials, O rings, belts and the like. Morespecifically, they can be used as decorations for lights, waterproofingpacking materials, vibration damping rubbers, packing materials forprotection against insects, vibration-damping, sound-insulating andairtight-sealing materials for cleaners, parts for water warmers, suchas covers for protecting them against water drops, water-tight packingmaterials, packing materials for heater parts, packing materials forelectrode parts and safety valve diaphragms, parts for sake warmers,such as hoses, watertight packing materials and electromagnetic valves,parts for steam oven ranges and rice cookers, such as watertight packingmaterials, water tank packing materials, suction pumping valves, bucketpacking materials, connecting hoses, belts, and heat-retaining heaterpacking materials, and parts for combustion apparatus (for example,steam diffuser seals), such as oil packing materials O rings, drainpacking materials, pressure tubes, blast tubes, air feeder/suctionpacking materials, vibration damping rubbers, fuel filler packingmaterials, fuel level indicator packing materials, fuel pipes, diaphragmvalves, air-supplying pipes and so forth as well as speaker gaskets,speaker edges, turntable sheets, belts, pulleys and the like foracoustic apparatus, among others. In the field of building andconstruction, they can be used as or in structural gaskets (zippergaskets), air membrane structure roofing materials, waterproofingmaterials, shaped sealing materials, vibration dampers, soundinsulators, setting blocks, sliders and so on. In the field of sports,they can be used as or in sports floors such as all weather pavementsand gymnasium floors, in the field of sports shoes, as sole materialsand insole materials and, in the field of ball games, as golf balls andso on. In the vibration damping rubber field, they can be used asvibration damping rubbers for automobiles, vibration damping rubbers forrailroad vehicles, vibration damping materials for airplanes, fenders,and so on. In the field of marine and civil engineering, they can beused as structural materials such as rubber expansion joints, bearingstructures, water sealing plates, waterproofing sheets, rubber dams,elastic pavement materials, vibration damping pads, guard or protectivestructures, etc., supplementary building and construction materials suchas rubber molds, rubber packers, rubber skirts, sponge mats, mortarhoses, mortar strainers, etc., and auxiliary building and constructionmaterials such as rubber sheets, air hoses, etc., safety precautionarticles such as rubber buoys, wave absorbing structures, etc., andenvironmental conservation goods such as oil fences, silt fences,antifouling materials, marine hoses, dressing hoses, oil skimmers and soforth. Furthermore, they may be used as plate or sheet rubbers, mats,foamed plates, etc.

BEST MODES FOR CARRYING OUT THE INVENTION

The following specific examples illustrate the present invention. Theyare by no means limitative of the scope of the present invention,however. The adsorbents used in the examples or comparative examples aresummarized in Table 1.

TABLE 1 Adsorbent types and species used Adsorbent ProductClassification Activated carbon Product of Wako Pure Chemical IndustriesActivated terra alba Galleon Earth V2 Acidic (product of MizusawaIndustrial Chemicals) adsorbent Aluminum silicate Kyowaad 700 series(SN, SL, PEL) Acidic Al₂O₃.9SiO₂.H₂O (product of Kyowa Chemical)adsorbent Magnesium silicate Mizukalife P-1G Acidic (product of MizusawaIndustrial Chemicals) adsorbent Aluminum hydroxide Kyowaad 200 Basic Al(OH)₃.XH₂O (product of Kyowa Chemical) adsorbent Magnesium oxideKyowamag 150 Basic MgO (product of Kyowa Chemical) adsorbentHydrotalcite species Kyowaad 500 series Basic Mg₆Al₂(OH)₁₆CO₃.4H₂O (PL,SH) (product of Kyowa Chemical) adsorbent Hydrotalcite species Kyowaad1000 Basic Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂O (product of Kyowa Chemical)adsorbent Hydrotalcite species Kyowaad 2000 BasicMg_(0.7)Al_(0.3)O_(1.15) (product of Kyowa Chemical) adsorbent Activatedalumina Product of Basic Wako Pure Chemical Industries adsorbent

PRODUCTION EXAMPLE 1 Method of Producing an Alkenyl-terminated VinylPolymer

A 10-L separable flask equipped with a reflux condenser and a stirrerwas charged with CuBr (42.0 g, 0.29 mol), and the reaction vessel insidewas purged with nitrogen. Acetonitrile (559 mL) was added, and thecontents were stirred on an oil bath at 70° C. for 45 minutes. Theretowere added butyl acrylate (1.00 kg), diethyl 2,5-diboromoadipate (175 g,0.488 mol) and pentamethyldiethylenetriamine (hereinafter referred to as“triamine” for short)(4.00 mL, 19.2 mmol), and the reaction was therebystarted. After the lapse of 60 minutes after the start of reaction,butyl acrylate (4.00 kg) was added dropwise continuously over 190minutes while heating at 70° C. with stirring. During the dropping ofbutyl acrylate, triamine (4.00 mL, 19.2 mmol) was added. After thesubsequent 60 minutes of heating at 70° C. with stirring, 1,7-octadiene(1.44 L, 9.75 mol) and triamine (20.5 mL, 0.0974 mol) were added, andthe heating at 70° C. was continued with stirring for 210 minutes.

The volatile matter was distilled off from the reaction mixture underreduced pressure, the residue was dissolved in hexane, and the solidmatter was filtered off to give an alkenyl-terminatedpolymer (polymer[1]). The polymer [1] had a number average molecular weight of 14,000 asdetermined by GPC measurement (polystyrene equivalent basis) with amolecular weight distribution of 1.34. The average number of alkenylgroups introduced per polymer molecule as determined by ¹H NMR analysiswas 2.5.

PRODUCTION EXAMPLE 2 Method (1) of Br Treatment of theAlkenyl-terminated Vinyl Polymer

A reaction vessel was charged with the polymer [1] (10 g) obtained inProduction Example 1 and potassium benzoate (0.57 g),N,N-dimethylacetamide (10 mL, hereinafter referred to as “DMAC”) wasadded, and the mixture was heated at 100° C. with stirring in a nitrogenatmosphere for 4 hours. The DMAC was distilled off with heating underreduced pressure, and toluene was added to the mixture thus obtained.The solid matter was filtered off, and the filtrate was concentrated togive a bromine group-free polymer (polymer [2]).

PRODUCTION EXAMPLE 3 Method (2) of Br Treatment of theAlkenyl-terminated Vinyl Polymer

A reaction vessel was charged with the polymer [1] (300 g) obtained inProduction Example 1 and potassium acetate (6.68 g), DMAC(300 mL) wasadded, and the mixture was heated at 100° C. with stirring in a nitrogenatmosphere for 8 hours. The DMAC was distilled off with heating underreduced pressure, and toluene was added to the mixture thus obtained.The solid matter was filtered off, and the filtrate was concentrated togive a bromine group-free polymer (polymer [3]).

EXAMPLE 1

Adsorption Treatment

The polymer [1] (5.0 g) was dissolved in toluene (15 mL). To thesolution were added a hydrotalcite adsorbent (0.25 g; Kyowaad 500PL,product of Kyowa Chemical) as a basic adsorbent, and magnesium silicate(0.25 g; Mizukalife P-1G, product of Mizusawa Industrial Chemicals) asan acidic adsorbent. The mixture was then heated at 100° C. withstirring for 1 hour. Dilution with toluene, separation of the adsorbentsby filtration and concentration of the filtrate gave a vinyl polymer.

Curing Test

The polymer after adsorption treatment was manually blended with alinear siloxane having, in each molecule, 5 hydrosilyl groups on averageand 5 α-methylstyrene groups on average (Si—H value: 3.70 mmol/g) and axylene solution of zero-valentplatinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex (platinumconcentration 1.3×10⁻⁵ mmol/μl) at room temperature, whereby ahydrosilylation reaction-susceptible composition was obtained. Theamount of the linear siloxane used was such that the alkenylgroup-to-hydrosilyl group mole ratio amounted to 1/1.5, and the amountof the platinum catalyst was expressed in terms of the mole ratio to thealkenyl group.

A portion of the composition was heated on a hot plate at 130° C. withstirring in an air atmosphere, and the gelation time was measured. Theresults are shown in Table 2.

Residual Copper Quantification

The polymer after adsorption treatment was mixed with ultrahigh puritynitric acid and ultrahigh purity sulfuric acid, and the mixture wassubjected to microwave decomposition. The residual copper in thedecomposition product was assayed using an ICP mass spectrometer(Yokogawa Analytical Systems model HP-4500), and the residual copper inthe polymer was quantified. The result is shown in Table 2.

EXAMPLE 2

Following the same procedures as in Example 1, polymer adsorptiontreatment, curing test of the polymer obtained by adsorption treatment(gelation time measurement) and quantification of the residual copper inthe polymer was carried out. The polymer subjected to adsorptiontreatment, the adsorbents used, amounts of the adsorbents, the curingtest results (gelation times) and the residual copper content are shownin Table 2.

COMPARATIVE EXAMPLE 1

Adsorption Treatment

The polymer [1] (5.0 g) was dissolved in toluene (15 mL). To thesolution was added activated terra alba (0.50 g; Galleon Earth V2,product of Mizusawa Industrial Chemicals) as an acidic adsorbent. Themixture was then heated at 100° C. with stirring for 1 hour. Dilutionwith toluene, separation of the adsorbent by filtration and removal ofthe toluene by distillation gave a vinyl polymer.

Curing Test

The polymer after adsorption treatment was subjected to curing testaccording to the same procedure as in Example 1, and the gelation timeswere measured. The results are shown in Table 2.

Residual Copper Quantification

Following the same procedure as in Example 1, the polymer afteradsorption treatment was assayed for residual copper in the polymer. Theresult is shown in Table 2.

COMPARATIVE EXAMPLES 2 to 12

Following the same procedures as in Comparative Example 1, polymeradsorption treatment, test curing of the polymers obtained by adsorptiontreatment (gelation time measurement) and quantification of the residualcopper in the polymers were carried out. The polymers subjected toadsorption treatment, the adsorbents used, amounts of the adsorbents,the curing test results (gelation times) and the residual coppercontents are shown in Table 2.

TABLE 2 Curing test Polymer Gelation time (sec) subjected Platinumcatalyst Residual to Amount of adsorbent used addition amount copperadsorption (wt % relative to 10⁻² 5 × 10⁻³ 2 × 10⁻³ content Exampletreatment Adsorbent polymer) eq eq eq (ppm) Example 1 Polymer Kyowaad500PL 5/5 10 30 4.0 [1] /Mizukalife P-1G Example 2 Polymer Kyowaad 500SH5/5 10 8.4 [3] /Kyowaad 700SL Compar. Polymer Galleon Earth Ex. 1 [1] V210 80 >120 >120 140 Compar. Polymer Kyowaad Ex. 2 [1] 700SN 1050 >120 >120 110 Compar. Polymer Kyowaad 10 20 40 >120 100 Ex. 3 [1]700SL Compar. Polymer Kyowaad 10 10 40 >120 46 Ex. 4 [1] 700PEL Compar.Polymer Mizukalife 10 20 >120 22 Ex. 5 [1] P-1G Compar. Polymer Kyowaad10 60 >120 >120 22 Ex. 6 [1] 200 Compar. Polymer Kyowamag 1040 >120 >120 11 Ex. 7 [1] 150 Compar. Polymer Kyowaad 10 30 80 >120 1.5Ex. 8 [1] 500PL Compar. Polymer Kyowaad Ex. 9 [1] 500SH 10 60 >120 >120Compar. Polymer Kyowaad 10 90 >120 >120 Ex. 10 [1] 1000 Compar. PolymerKyowaad 10 30 >120 >120 11 Ex. 11 [1] 2000 Compar. Polymer Kyowaad 1020 >120 Ex. 12 [3] 700PEL *“>120” means “not yet cured after 120seconds”.

The results shown in Table 2 indicate the following. When an acidicadsorbent alone is used, the residual copper content was high and theamount of the platinum catalyst as required for the manifestation ofcurability was as large as 5×10⁻³ to 10⁻² equivalent (ComparativeExamples 1 to 5 and 12). When a basic adsorbent alone was used, theresidual copper content was low but the amount of the platinum catalystas required for the manifestation of curability was as large as 5×10⁻³to 10⁻² equivalent (Comparative Examples 6 to 11). On the contrary, whenthe adsorption treatment was carried out using the acidic adsorbent andbasic adsorbent combinedly, the amount of the platinum catalyst requiredfor gelation was small and the residual copper content was also low. Inparticular when a hydrotalcite adsorbent and aluminum silicate were usedin combination, curability was shown at a platinum catalyst amount of2×10⁻³ equivalents.

PRODUCTION EXAMPLE 4 Method of Producing an Alkenyl-terminated VinylPolymer

A 10-L separable flask equipped with a reflux condenser and a stirrerwas charged with CuBr (42.0 g, 0.29 mol), and the reaction vessel insidewas purged with nitrogen. Acetonitrile (559 mL) was added, and thecontents were stirred on an oil bath at 70° C. for 45 minutes. Theretowere added butyl acrylate (1.00 kg), diethyl 2,5-dibromoadipate (175 g,0.488 mol) and pentamethyldiethylenetriamine (hereinafter referred to as“triamine”)(4.00 mL, 19.2 mmol), and the reaction was thereby started.After the lapse of 60 minutes after the start of reaction, butylacrylate (4.00 kg) was added dropwise continuously over 190 minuteswhile heating at 70° C. with stirring. During the dropping of butylacrylate, triamine (4.00 mL, 19.2 mmol) was added. After the subsequent60 minutes of heating at 70° C. with stirring, 1,7-octadiene (1.44 L,9.75 mol) and triamine (20.5 mL, 0.0974 mol) were added, and the heatingat 70° C. was continued with stirring for 210 minutes.

The volatile matter was distilled off from the reaction mixture underreduced pressure, the residue was dissolved in hexane, and the solidmatter was filtered off to give an alkenyl-terminatedpolymer (polymer[4]). The polymer [4] had a number average molecular weight of 13,000 asdetermined by GPC measurement (polystyrene equivalent basis) with amolecular weight distribution of 1.23. The average number of alkenylgroups introduced per polymer molecule as determined by ¹H NMR analysiswas 1.5.

PRODUCTION EXAMPLE 5 Method of Br Treatment of the Alkenyl-terminatedVinyl Polymer

A reaction vessel was charged with the polymer [4] (300 g) obtained inProduction Example 4 and potassium acetate (6.68 g), DMAC(300 mL) wasadded, and the mixture was heated at 100° C. with stirring in a nitrogenatmosphere for 8 hours. The DMAC was distilled off with heating underreduced pressure, and toluene was added to the mixture thus obtained.The solid matter was filtered off, and the filtrate was concentrated togive a bromine group-free polymer (polymer [5]).

EXAMPLE 3 Reduction of Diluent Solvent Amount in the Step of AdsorptionTreatment

Adsorption Treatment

The polymer [5] (3.0 g) was mixed with toluene (0.30 g) To the mixturewere added a hydrotalcite adsorbent (0.030 g; Kyowaad 500SH, product ofKyowa Chemical) and aluminum silicate (0.030 g; Kyowaad 700SL, productof Kyowa Chemical). The mixture was then heated at 110° C. with stirringfor 1 hour. Dilution with toluene, separation of the adsorbents byfiltration and removal of the toluene by distillation gave a vinylpolymer.

Curing Test

The polymer after adsorption treatment was subjected to curing testaccording to the same procedure as in Example 1, and the gelation timeswere measured. The results are shown in Table 4.

Residual Copper Quantification

Following the same procedure as in Example 1, the polymer afteradsorption treatment was assayed for residual copper therein. The resultis shown in Table 4.

EXAMPLES 4 to 8

Following the same procedures as in Example 3, polymer adsorptiontreatment, curing testing of the polymers obtained by adsorptiontreatment (gelation time measurement) and quantification of the residualcopper in the polymers were carried out. The polymers treated, andadsorption treatment conditions (adsorbents used, adsorbent amounts,solvents used, polymer concentrations, temperatures, periods) are shownin Table 3. The curing test results (gelation times) and the residualcopper contents are shown in Table 4.

TABLE 3 Adsorption treatment conditions Total amount of adsorbentsused¹⁾ Polymer wt % concentration²⁾ Temperature Period Polymer Adsorbent(relative to polymer) Solvent wt % ° C. Hr Example 3 PolymerKyowaad500SH/ 2 Toluene 91 110 1 [5] Kyowaad700SL Example 4 PolymerKyowaad500SH/ 2 Xylene 91 130 3 [5] Kyowaad700SL Example 5 PolymerKyowaad500SH/ 2 None 100 130 3 [5] Kyowaad700SL Example 6 PolymerKyowaad500SH/ 2 None 100 150 6 [5] Kyowaad700SL Example 7 PolymerKyowaad500SH/ 10 Toluene 54 100 1 [5] Kyowaad700SL Example 8 PolymerKyowaad500SH/ 10 Toluene 54 100 3 [5] Kyowaad700SL ¹⁾Total amount ofadsorbents used: Total weight of Kyowaad 500SH and Kyowaad 700SL used.²⁾Polymer concentration = (polymer weight/ (polymer weight + solventweight)) × 100

TABLE 4 Adsorption treatment results Re- sidual Gelation time (sec)copper Amount of platinum catalyst content 2 × 10⁻³ eq 10⁻³ eq 5 × 10⁻⁴eq 3 × 10⁻⁴ eq (ppm) Example 3 70 130 60.0 Example 4 10 70 14.0 Example5 10 60 12.0 Example 6 <5 30 100 8.6 Example 7 10 >120 Example 8 <5 >1208.4 ¹⁾“>120” means “not yet cured after 120 seconds”. ²⁾Platinumcatalyst addition level is the mole ratio to the alkenyl group.

PRODUCTION EXAMPLE 6 Method of Producing an Alkenyl-terminated VinylPolymer (Copolymer) and Method of Br Treatment

A 10-L separable flask equipped with a reflux condenser and a stirrerwas charged with CuBr (36.02 g, 0.2511 mol), and the reaction vesselinside was purged with nitrogen. Acetonitrile (618 mL) was added, andthe contents were stirred on an oil bath at 70° C. for 15 minutes.Thereto were added butyl acrylate (360 mL, 2.51 mol), ethyl acrylate(500 mL, 4.62 mol), 2-methoxyethyl acrylate (375 mL, 2.91 mol), diethyl2,5-diboromoadipate (150.68 g, 0.419 mol) andpentamethyldiethylenetriamine (hereinafter referred to as“triamine”)(2.18 mL, 1.81 g, 10.46 mmol), and the reaction was therebystarted. While heating at 70° C. with stirring, a mixture composed ofbutyl acrylate (1,440 mL), ethyl acrylate (2,002 mL) and 2-methoxyethylacrylate (1,498 mL) was added dropwise continuously over 210 minutes.During the dropping of the monomer mixture, triamine (7.63 mL, 6.33 g,36.5 mmol) was added. After the lapse of 330 minutes after start of thereaction, 1,7-octadiene (1,236 mL, 922 g, 8.37 mol) and triamine (26.16mL, 21.71 g, 0.125 mol) were added, and the heating at 70° C. withstirring was continued for 250 minutes.

The reaction mixture was diluted with toluene and passed through anactivated alumina column, and the volatile matter was then distilled offunder reduced pressure to give an alkenyl-terminated copolymer{alkenyl-terminated poly(butyl acrylate, ethyl acrylate, methoxyethylacrylate); hereinafter referred to as copolymer [1]}.

A 10-L separable flask equipped with a reflux column was charged withthe copolymer [1] (2.87 kg), potassium acetate (79.57 g) andN,N-dimethylacetamide (2.9 L), and the mixture was heated at 100° C.with stirring under a nitrogen stream for 12 hours. TheN,N-dimethylacetamide was removed by heating under reduced pressure, andthe residue was diluted with toluene. The toluene-insoluble matter (KBrand excess potassium acetate) was filtered off using an activatedalumina column. The volatile matter was distilled off from the filtrateunder reduced pressure to give a copolymer (copolymer [2]).

EXAMPLE 9 Adsorption Treatment of the Copolymer, Preparation of aHydrosilylation Reaction-susceptible Composition and Production of CuredProducts

A 10-L separable flask equipped with a reflux column was charged withthe copolymer [2] (2.87 kg), aluminum silicate (143 g, Kyowaad 700SL,product of Kyowa Chemical), a hydrotalcite adsorbent (143 g, Kyowaad500SH, product of Kyowa Chemical) and. toluene (5.2 L), and the mixturewas heated at 100° C. under a nitrogen stream for 7 hours. Theadsorbents were filtered off, and the toluene was distilled off from thefiltrate under reduced pressure to give a vinyl group-terminatedcopolymer (copolymer [3]). The copolymer obtained had a number averagemolecular weight of 18,000 as determined by GPC measurement (polystyreneequivalent basis) with a molecular weight distribution of 1.24. Theaverage number of vinyl groups introduced per copolymer molecule asdetermined by ¹H NMR analysis was 2.2.

The copolymer [3] (alkenyl group content 0.158 mmol/g) was uniformlyblended with a linear siloxane (containing, in each molecule, 5hydrosilyl groups on average and 5 α-methylstyrene groups on average;Si—H group amount 3.70 mmol/g). The resulting mixture was uniformlyblended with the 1,3-divinyl-1,1,3,3-tetramethyldisiloxane-platinumcomplex catalyst (1.3×10⁻⁵ mmol/μl solution in xylene). The amount ofthe linear siloxane was selected at a level such that the SiH groups ofthe linear siloxane amounted to 2.32 equivalents relative to the alkenylgroups of the copolymer [3], and the amount of the platinum catalyst ata level such that the mole ratio thereof to the alkenyl group amountedto 6.5×10⁻⁴ equivalents. A portion of the thus-obtained hydrosilylationreaction-susceptible composition was heated at 150° C., and the gelationtime was measured. It was 14 seconds. The hydrosilylationreaction-susceptible composition was poured into a mold and heated at150° C., whereby a cured product having rubber elasticity was obtained.

PRODUCTION EXAMPLE 7

A 10-L separable flask equipped with a reflux condenser and a stirrerwas charged with CuBr (50.4 g, 0.35 mol), and the reaction vessel insidewas purged with nitrogen. Acetonitrile (670 mL) was added, and thecontents were stirred on an oil bath at 70° C. for 30 minutes. Theretowere added butyl acrylate (1.20 kg), diethyl 2,5-dibromoadipate (105 g,0.29 mol) and pentamethyldiethylenetriamine (hereinafter referred to as“triamine”)(2.44 mL, 11.7 mmol), and the reaction was thereby started.While heating at 70° C. with stirring, butyl acrylate (4.80 kg) wasadded dropwise continuously. During the dropping of butyl acrylate,triamine (9.8 mL, 47 mmol) was added. After the subsequent heating at70° C. with stirring, 1,7-octadiene (1.73 L) and triamine (18.3 mL, 88mmol) were added, and the heating at 70° C. was further continued withstirring for 4 hours.

The reaction mixture was diluted with toluene, and the insoluble matterwas filtered off. The filtrate was concentrated to give analkenyl-terminated polymer (polymer [6]). The polymer [6] had a numberaverage molecular weight of 25,700 as determined by GPC measurement(polystyrene equivalent basis) with a molecular weight distribution of1.30. The average number of alkenyl groups introduced per polymermolecule as determined by ¹H NMR analysis was 2.6.

A reaction vessel was charged with the polymer [6] (392 g) and potassiumacetate (7.7 g), DMAC. (400 mL) was added, and the mixture was heated at100° C. with stirring in a nitrogen atmosphere for 10 hours. The DMACwas distilled off with heating under reduced pressure, and toluene wasadded to the mixture thus obtained. The solid matter was filtered off,and the filtrate was concentrated to give a bromine group-free polymer(polymer [7]).

EXAMPLE 10

The polymer [7] (300 g) obtained in Production Example 7 was mixed withtoluene (30 mL). To the mixture were added a hydrotalcite adsorbent (3.0g; Kyowaad 500SH, product of Kyowa Chemical) as a basic adsorbent andaluminum silicate (3.0 g; Kyowaad 700SL, product of Kyowa Chemical) asan acidic adsorbent. The mixture was then heated at 150° C. withstirring for 3 hours. Dilution with toluene, separation of theadsorbents by filtration and concentration of the filtrate gave apolymer (polymer [8]).

The polymer [8] was manually blended with a linear siloxane having, ineach molecule, 5 hydrosilyl groups on average and 5 α-methylstyrenegroups on average (Si—H value: 3.70 mmol/g) and a xylene solution ofzero-valent platinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex(platinum concentration 1.3×10⁻⁵ mmol/μl) at room temperature, whereby ahydrosilylation reaction-susceptible composition was obtained. Theamount of the linear siloxane used was such that the alkenylgroup-to-hydrosilyl group mole ratio amounted to 1/1.5, and the amountof the platinum catalyst was such that the mole ratio thereof to thealkenyl group amounted to 10⁻³ equivalent. A portion of thethus-obtained composition was heated at 130° C., and the gelation timewas measured. It was 40 seconds.

EXAMPLE 11 Method of Producing an Alkoxysilyl Group-terminated VinylPolymer

The polymer [8] (30 g) obtained in Example 10 was heated at 100° C.while reducing the pressure. After restoring normal pressure withnitrogen, methyl orthoformate (0.33 mL, 3.0 mmol) and a xylene solutionof zero valent platinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxanecomplex (1.13 mL; platinum concentration 1.3×10⁻⁵ mmol/μl) were added,followed by mixing up, under a nitrogen stream. After pressurization to1.5 MPa with nitrogen, the mixture was heated at 100° C. with stirringfor 2 hours. The volatile matter was removed under heating to give analkoxysilyl group-containing polymer (polymer [9]). The polymer [9] hada number average molecular weight of 33,300 as determined by GPCmeasurement (polystyrene equivalent basis) with a molecular weightdistribution of 1.62. The average number of silyl groups introduced perpolymer molecule as determined by ¹H NMR analysis was 1.7.

EXAMPLE 12 Method of Producing a Cured Product

The polymer [9] obtained in Example 11 was mixed up with a tetravalenttin catalyst (dibutyltin diacetylacetonate) to give a curablecomposition. When allowed to stand at room temperature for 6 hours, thecomposition gave a cured product having rubber elasticity.

EXAMPLE 13 Combined Use of Another Adsorbent

The polymer [7] (5.6 g) obtained in Production Example 7 was blendedwith xylene (0.56 g). To the mixture were added activated carbon (0.037g; product of Wako Pure Chemical Industries, powder form), ahydrotalcite adsorbent (0.037 g; Kyowaad 500SH, product of KyowaChemical) and aluminum silicate (0.037 g; Kyowaad 700SL, product ofKyowa Chemical), and the mixture was heated at 150° C. with stir ringfor 3 hours. Dilution with toluene, adsorbent removal by filtration andconcentration of the filtrate gave a polymer (polymer [10]).

The polymer [10] was subjected to test curing in the same manner as inExample 1, and the gelation times were measured. When the platinumcatalyst was used in an amount of 5×10⁻⁴ equivalents relative to thealkenyl group, the gelation time at 130° C. was 40 seconds.

PRODUCTION EXAMPLE 8

A 10-L separable flask equipped with a reflux condenser and a stirrerwas charged with CuBr (50.4 g, 0.35 mol), and the reaction vessel insidewas purged with nitrogen. Acetonitrile (670 mL) was added, and thecontents were stirred on an oil bath at 70° C. for 30 minutes. Theretowere added butyl acrylate (1.20 kg), diethyl 2,5-dibromoadipate (105 g,0.29 mol) and pentamethyldiethylenetriamine (hereinafter referred to as“triamine”)(2.44 mL, 11.7 mmol), and the reaction was thereby started.While heating at 70° C. with stirring, butyl acrylate (4.80 kg) wasadded dropwise continuously. During the dropping of butyl acrylate,triamine (9.8 mL, 47 mmol) was added. After the subsequent heating at70° C. with stirring, 1,7-octadiene (1.73 L) and triamine (18.3 mL, 88mmol) were added, and the heating at 70° C. was continued with stirringfor further 4 hours. The reaction mixture was diluted with toluene, andthe solid matter was filtered off. Concentration of the filtrate gave analkenyl group-terminated polymer (polymer [11]). The polymer [11] had anumber average molecular weight of 26,600 as determined by GPCmeasurement (polystyrene equivalent basis) with a molecular weightdistribution of 1.27. The average number of alkenyl groups introducedper polymer molecule as determined by ¹H NMR analysis was 2.7.

EXAMPLE 14 Adsorption Treatment in the Presence of Br Treatment Agentsand an Inorganic Salt

A reaction vessel was charged with the polymer [11] (625 g) obtained inProduction Example 8 and potassium acetate (12.3 g), DMAC(600 mL) wasadded, and the mixture was heated at 100° C. with stirring in a nitrogenatmosphere for 10 hours. The DMAC was distilled off with heating underreduced pressure to give a mixture (mixture [1]) of the polymer,potassium acetate and KBr.

The mixture [1] (300 g) was mixed with xylene (30 g). To the mixture wasadded a hydrotalcite adsorbent (1.5 g; Kyowaad 500SH, product of KyowaChemical), and the mixture was heated at 150° C. with stirring. Fifteenminutes later, Kyowaad 500SH (1.5 g) was added and, 30 minutes later,aluminum silicate (1.5 g; Kyowaad 700SL, product of Kyowa Chemical) wasadded and, after further 45 minutes, Kyowaad 700SL (1.5 g) was added.The mixture was further heated at 150° C. with stirring (the totalheating period being 3 hours). The mixture was diluted with toluene, theadsorbents were filtered off, and the filtrate was concentrated to givea polymer (polymer [12]).

The polymer [12] was subjected to test curing in the same manner as inExample 1. When the platinum catalyst was used in an amount of 8×10⁻⁴equivalents (mole ratio to the alkenyl group), the gelation time at 130°C. was 40 seconds.

EXAMPLE 15

The mixture [1] obtained in Example 14 was diluted with toluene, thepotassium acetate and KBr were filtered off, and the filtrate wasconcentrated to give a polymer (polymer [13]). The polymer [13] (254 g)was mixed with xylene (2.54 g). To the mixture was added a hydrotalciteadsorbent (1.5 g; Kyowaad 500SH, product of Kyowa Chemical), and themixture was heated at 150° C. with stirring. Fifteen minutes later,Kyowaad 500SH (1.5 g) was added and, 30 minutes later, aluminum silicate(1.5 g; Kyowaad 700SL, product of Kyowa Chemical) was added and, afterfurther 45 minutes, Kyowaad 700SL (1.5 g) was added. The mixture wasfurther heated at 150° C. with stirring (the total heating period being3 hours). The mixture was diluted with toluene, the adsorbents werefiltered off, and the filtrate was concentrated to give a polymer(polymer [14]).

The polymer [14] was subjected to test curing in the same manner as inExample 1, and the gelation times were measured. When the platinumcatalyst was used in an amount of 8×10⁻⁴ equivalents (mole. ratio to thealkenyl group), the gelation time at 130° C. was 90 seconds.

EXAMPLE 16

Methyl orthoformate (3.0 mL, 27 mmol) and a xylene solution of zerovalent platinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex (0.20mL; platinum concentration 1.3×10⁻⁴ mmol/μl) were admixed with thepolymer [12] (270 g) obtained in Example 14. After 3 hours of heating at100° C. with stirring, a xylene solution of zero valentplatinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex (0.40 mL;platinum concentration 1.3×10⁻⁴ mmol/μl) was further added. The mixturewas further heated at 100° C. with stirring for 3 hours. The volatilematter was removed from the mixture to give an alkoxysilylgroup-containing polymer (polymer [15]). The average number of silylgroups introduced per polymer molecule as determined by ¹H NMR analysiswas 1.8.

EXAMPLE 17

The polymer [15] obtained in Example 16 was mixed up with a tetravalenttin catalyst (dibutyltin diacetylacetonate) to give a curablecomposition. When allowed to stand at room temperature for 2 days andthen heated at 50° C. for 3 days, the composition gave a cured producthaving rubber elasticity.

INDUSTRIAL APPLICABILITY

In accordance with the present invention, vinyl polymers obtainable byatom transfer radical polymerization can be purified economically andefficiently by adsorption treatment using an acidic adsorbent and abasic adsorbent combinedly, with the result that the reactivity inhydrosilylation thereof is improved. Thus, the polymers can be used ascomponents in hydrosilylation reaction-susceptible compositions.

1. A method of purifying a vinyl polymer obtained by atom transferradical polymerization of a vinyl monomer(s) using a transition metalcomplex as a polymerization catalyst which method comprises bringing thevinyl polymer into contact with an acidic adsorbent and a basicadsorbent in a total amount of 0.01 to 10 parts by weight per 100 partsby weight of the vinyl polymer, wherein the acidic adsorbent and/orbasic adsorbent is at least one member selected from the groupconsisting of activated carbon, a synthetic resin adsorbent, and aninorganic adsorbent.
 2. The method of purifying a vinyl polymeraccording to claim 1, wherein the acidic adsorbent and/or basicadsorbent is an inorganic adsorbent.
 3. The method of purifying a vinylpolymer according to claim 1, wherein the acidic adsorbent is activatedterra alba or aluminum silicate.
 4. The method of purifying a vinylpolymer according to claim 1, wherein the acidic adsorbent is aluminumsilicate.
 5. The method of purifying a vinyl polymer according to claim1, wherein the basic adsorbent is activated alumina or a hydrotalcite.6. The method of purifying a vinyl polymer according to claim 1, whereinthe basic adsorbent is a hydrotalcite.
 7. The method of purifying avinyl polymer according to claim 1, wherein a solution of the vinylpolymer with a vinyl polymer concentration of not less than 90% byweight is brought into contact with an acidic adsorbent and/or a basicadsorbent.
 8. The method of purifying a vinyl polymer according to claim1, wherein the vinyl polymer is brought into contact with an acidicadsorbent and/or a basic adsorbent without using any solvent.
 9. Themethod of purifying a vinyl polymer according to claim 1, wherein thevinyl polymer has a halogen group.
 10. The method of purifying a vinylpolymer according to claim 1, wherein the vinyl polymer has an alkenylgroup.
 11. The method of purifying a vinyl polymer according to claim 1,wherein the vinyl polymer is one obtained by producing a halogengroup-containing vinyl polymer by atom transfer radical polymerizationand converting the halogen group to a substituent other than the halogengroup by a nucleophilic substitution reaction.
 12. The method ofpurifying a vinyl polymer according to claim 11, wherein the vinylpolymer is brought into contact with an acidic adsorbent and/or a basicadsorbent without removing, from the polymer, the unreacted nucleophilicreagent and/or the halide resulting from the nucleophilic substitutionreaction.
 13. The method of purifying a vinyl polymer according to claim1, wherein the central atom of the transition metal complex is copper.14. The method of purifying a vinyl polymer according to claim 1,wherein a triamine compound is used as a ligand to the catalyst in theatom transfer radical polymerization.
 15. The method of purifying avinyl polymer according to claim 1, wherein the acidic adsorbent andbasic adsorbent are used in total amount of 0.1 to 10 parts by weightper 100 parts by weight of the vinyl polymer.
 16. A vinyl polymer whichis obtained byte method of purifying a vinyl polymer according toclaim
 1. 17. A hydrosilylation reaction-susceptible composition whichcomprises (A) the vinyl polymer according to claim
 16. 18. Ahydrosilylation reaction-susceptible composition which comprises (A) thevinyl polymer according to claim 16 and (B) a hydrosilylgroup-containing compound.
 19. A hydrosilylation reaction-susceptiblecomposition which comprises (A) the vinyl polymer according to claim 16,(B) a hydrosilyl group-containing compound and (C) a platinum catalyst.20. A vinyl polymer which is obtained by subjecting the hydrosilylationreaction-susceptible composition according to claim 17 tohydrosilylation.
 21. A crosslinkable silyl group-containing vinylpolymer which is obtained by subjecting the hydrosilylationreaction-susceptible composition according to claim 17 tohydrosilylation.
 22. A cured product which is obtained by subjecting thehydrosilylation reaction-susceptible composition according to claim 17to hydrosilylation.
 23. A molded article which is obtained by subjectingthe hydrosilylation reaction-susceptible composition according to claim17 to hydrosilylation.
 24. A method of producing vinyl polymers whichcomprises using the method of purifying a vinyl polymer according toclaim
 1. 25. The method of purifying a vinyl polymer according to claim1, wherein the synthetic resin adsorbent is an ion exchange resin. 26.The method of purifying a vinyl polymer according to claim 1 or 2,wherein the inorganic adsorbent is at least one member selected from thegroup consisting of silicon dioxide, magnesium oxide, silica gel,silica-aluminum, aluminum silicate, magnesium silicate, activatedalumina, aluminum hydroxide, acidic terra alba, activated terra alba, azeolite adsorbent, dawsonite compound, a hydrotalcite, and a calcinedhydrotalcite.